CN101910207A - Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability - Google Patents

Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability Download PDF

Info

Publication number
CN101910207A
CN101910207A CN200880125005XA CN200880125005A CN101910207A CN 101910207 A CN101910207 A CN 101910207A CN 200880125005X A CN200880125005X A CN 200880125005XA CN 200880125005 A CN200880125005 A CN 200880125005A CN 101910207 A CN101910207 A CN 101910207A
Authority
CN
China
Prior art keywords
acid
ester
methyl
ether
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200880125005XA
Other languages
Chinese (zh)
Other versions
CN101910207B (en
Inventor
A·泰尔努瓦尔
D·绍恩菲尔德
B·布鲁赫曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN101910207A publication Critical patent/CN101910207A/en
Application granted granted Critical
Publication of CN101910207B publication Critical patent/CN101910207B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to producing polymer dispersions with improved freeze/thaw stability by adding a highly-branched polymer thereto and the use of highly-branched polymers for the above.

Description

Highly-branched polymer is used to prepare the purposes of the polymeric dispersions with improved freeze/thaw stability
The present invention relates to a kind ofly have the method for the polymeric dispersions of improved freezing-thaw stability, also relate to the purposes that highly-branched polymer is used for this purpose by in polymeric dispersions, adding the highly-branched polymer preparation.
When being exposed to the following time of temperature that existing water freezes, aqueous polymer dispersions and be easy to lose the application feature that needs based on the coating (paint) of this type of dispersion.The ice crystal that forms in this process causes latex particle at first in the remaining liq that still exists, concentrate at the ice intergranular at last.This can cause by associating or cohesion forms undesired big polymer beads, and is accompanied by viscosity usually and significantly increases.Often can not get original application character during thawing.This can store, transportation and processing aqueous polymer dispersions and bring problem during based on its coating.
Adding frostproofer in polymeric dispersions and latex coating is known to improve it to cryogenic tolerance.Suitable frostproofer is recorded in, Ullmann ' s Encyclopedia of Industrial Chemistry for example, and the 5th edition, the A3 volume is in the 23-31 page or leaf.They comprise the pure and mild alcohol ether of relative higher functionality, as ethylene glycol, glycol ether and propylene glycol.But use this organic hydrocarbon compound of volatility (VOC) that slowly is released into the environment from coating more and more to be out of favour.Therefore need be used to improve the non-volatile additive of the polymeric dispersions of freeze/thaw stability.
WO 2005/054384 has described a kind of resin composition for aqueous coating material that comprises small portion volatile organic compounds (VOC content) and have good freeze/thaw stability features.These coating materials (coating material) comprise a kind of aqueous dispersion based on multistage polymkeric substance (multistage polymer), and described multistage polymkeric substance comprises the polymerisable oxyalkylated surface active cpd of copolymerized form.
At present also do not know to add highly-branched polymer and be used to prepare polymeric dispersions purpose with improved freeze/thaw stability.This type of highly-branched polymer itself is known, in some cases also as the additive for preparing aqueous polymer dispersions.
WO 00/29495 has described a kind of coating material that comprises a kind of solvent, a kind of Synolac (vibrin) and a kind of star polymer.Star polymer in this type of material to improve the application feature of described coating material, for example is used to obtain lower viscosity as properties-correcting agent.They are derived from the multi-functional thiol who comprises at least three ethene formula unsaturated terminal chains.
WO 01/96411 has described the amphiphilic star polymer with the thiol group center of stretching out at least three polymeric arms from it, has also described the purposes that described star polymer is used for stabilized aqueous polymeric dispersions.
WO 2004/016700 has described can be by using at least a water base copolymer dispersion that obtains with the branch-shape polymer copolymerization of alkenyl functionalization.The copolymer dispersion that forms has obvious improvement block character.The document is not taught in and adds the purpose that highly-branched polymer is used to improve freeze/thaw character behind the emulsion polymerization in hydrotropisms's polymeric dispersions.
WO 2005/003186 has described the method for a kind of preparation based on the aqueous polymer dispersions of multipolymer, described multipolymer comprises at least a hydrophobic allyl group, vinyl, toxilic acid or diene monomers, and described being aggregated under at least a branch-shape polymer existence carried out.Branch-shape polymer in this system makes it possible to even uses the strong-hydrophobicity monomer of the water-soluble 0.001g/l of being lower than to be used for letex polymerization.Do not describe and use this type of branch-shape polymer to be added into polymeric dispersions to improve its freeze/thaw stability.
Z.Xu and W.T.Ford are at Journal of Polymer Science:Part A:Polymer Chemistry, the 41st volume, 597-605 (2003) and at Macromolecules2002,35, the polystyrene latex for preparing by aqueous emulsion polymerization in the presence of dodecanoyl sulfonamide derivatives that gathers (propyleneimine) branch-shape polymer and sodium lauryl sulphate has been described among the 7662-7668.C.Yi, Z.Xu and W.T.Ford be in Colloid.Polym.Sci. (2004), and 282, described in the 1054-1058 page or leaf according to the seed law (seed method) by emulsion polymerizing preparation (amido amine) branch-shape polymer/polystyrene composite emulsion.
An object of the present invention is to provide aqueous polymer dispersions with improved freeze/thaw stability.After freeze/thaw exposes, expect that described dispersion preferably has constant substantially application feature, as constant substantially viscosity, constant substantially granular size or particle size dispersion.Preferably under not using the situation that increases the additive of VOC content in the dispersion as far as possible, realize this target simultaneously.
Unexpectedly, have been found that this purpose can realize by using highly-branched polymer.
Therefore the present invention at first provides a kind of by at least a α, β-ethylenically unsaturated monomers M) free-radical emulsion polymerization and add at least a highly-branched polymer and prepare aqueous polymer dispersions PD with improved freeze/thaw stability) method.
It is a kind of by a kind of aqueous polymer dispersions PD that the present invention also provides), at least a highly-branched polymer and randomly at least a other film-forming polymer form or comprise the binder composition of above-mentioned substance.
The present invention also provides a kind of coating material of waterborne compositions form, and it comprises
-a kind of by a kind of aqueous polymer dispersions PD), a kind of highly-branched polymer and optional at least a other film-forming polymer form or comprise the binder composition of above-mentioned substance,
-optional at least a inorganic filler and/or at least a mineral dye,
-optional other auxiliary agent and
-water.
The present invention also provides highly-branched polymer to be used to improve the purposes of freeze/thaw stability as the additive of aqueous polymer dispersions.
The present invention also provides a kind of and has improved aqueous polymer dispersions PD by adding at least a highly-branched polymer) the method for freeze/thaw stability, described aqueous polymer dispersions PD) free-radical emulsion polymerization by at least a α, β-ethylenically unsaturated monomers M) obtains.
To described polymeric dispersions PD) in add described highly-branched polymer can be at preparation PD) letex polymerization before and/or in the process and/or carry out afterwards.The described highly-branched polymer of preferred interpolation is to carry out after letex polymerization.Add the part also comprise as product formulation and add after letex polymerization, described product comprises based at least a α, β-ethylenically unsaturated monomers M) emulsion polymer.For this purpose, can for example add in the coating as additive with undefined highly-branched polymer at least a.Therefore, the present invention also provides at least a highly-branched polymer as comprising the purposes that the product additive is used to improve the freeze/thaw stability of described product, described product comprises based at least a with undefined α, β-ethylenically unsaturated monomers M) emulsion polymer.Particularly, this relates to the purposes as paint additive.
The present invention also provides and has comprised the aqueous polymer dispersions PD of at least a highly-branched polymer as additive) as the purposes of coating composition.
Freeze/thaw stability is the parameter that the technician knows.The principle of determining freeze/thaw stability can adopt standard ISO 1147.The freeze/thaw stability of aqueous polymer dispersions can be determined according to ASTM D 2243-95 (checking and approving once more in 2003).According to this standard, described dispersion is placed-18 ℃ chill room 17 hours, to place 7 hours in room temperature (23 ℃) then, the freeze/thaw that forms 24 hours circulates.Next whether forming coagulum all detects.If no, so described latex dispersions is stable to coagulative formation, repeats above-mentioned circulation (freeze and melt), then reexamines coagulative formation.Continue the circulation of this freeze/thaw until or observe and form coagulum or maximum 5 circulations all do not form coagulum.
With described highly-branched polymer with preferred 0.1 weight % to the 20 weight % of the gross weight that accounts for highly-branched polymer and polymeric dispersions, more preferably the amount of 0.2 weight % to 15 weight %, more special 0.5 weight % to 10 weight % adds described polymeric dispersions PD).
The present invention uses described highly-branched polymer to have at least a in the following advantage:
-carry out the constant substantially viscosity of the dispersion that freeze/thaw expose to handle;
-carry out the constant substantially granular size and the particle size dispersion of the dispersion that freeze/thaw expose to handle;
-in the dispersion of carrying out freeze/thaw exposure processing, form coagulum hardly or not;
Even-also can process dispersion near zero pour;
The highly-branched polymer of-use and the highly compatible of multiple dispersion;
-at least partially or completely avoid using frostproofer, the VOC content of corresponding reduction dispersion.
Determining and can using rotational viscosimeter under 23 ℃ of temperature according to DIN EN ISO 3219 of viscosity for example uses Brookfield RVT viscometer to carry out; For example use axle #5 or use axle #4 with 20rpm with the speed of rotation of 10rpm.
Coagulative amount can for example be determined with the screen filtration polymeric dispersions with regulation screen size (for example 125 μ m) by expose the back in freeze/thaw.
According to the present invention, at least a highly-branched polymer is used to prepare polymeric dispersions PD).Be purpose of the present invention, statement " highly-branched polymer " typically refers to the polymkeric substance that is characterized as strong collateralization structure and high functionality most.For the General Definition of highly-branched polymer, also can be with reference to P.J.Flory, J.Am.Chem.Soc.1952,74,2718 and H.Frey etc., Chem.Eur.J.2000,6, No.14,2499 (different with the definition of selecting for use herein, they are called as " hyperbranched polymer " in described document).
Highly-branched polymer on the meaning of the present invention comprises star polymer, branch-shape polymer, arbor branch shape polymkeric substance (arborol), and different highly-branched polymer, particularly as hyperbranched polymer.
Star polymer is the polymkeric substance that wherein extends three or more chains from the center.This center can be single atom or atomic group.
Derived from star polymer, but on each independent chain, has the star side chain on the branch-shape polymer structure.The formation of branch-shape polymer is from small molecules, forms the side chain of higher quantity by continuous reaction repeated sequence, has functional group separately at the end of described side chain, itself then become the starting point of other side chain again.Therefore the quantity of monomer end group increases with index in each reactions steps, and final formation ideally is the spheric tree structure.The feature of branch-shape polymer is the quantity of the step of reaction (reaction order) of carrying out for its synthetic purpose.On its massiveness basis of (in the ideal case, all side chains comprise the monomeric unit of identical quantity), branch-shape polymer is monodispersed substantially, and promptly they have the molar mass of regulation usually.
Usually also be called as branch-shape polymer below the highly-branched polymer of molecule and even structure.
Opposite with above-mentioned branch-shape polymer, " hyperbranched polymer " in the context of the invention is the uneven highly-branched polymer of molecule and structure.They have length and collateralization with and different side chain and/or the side shoots of molar mass distribution (polydispersity).
The highly-branched polymer of the present invention preferably degree of branching of per molecule (DB) is 10% to 100%, more preferably 10% to 90%, more special 10% to 80%.Degree of branching DB is defined by following formula
DB (%)=(T+Z)/(T+Z+L) x100, wherein
T is the mean number of the terminal monomeric unit that connects,
Z is the mean number of the monomeric unit of formation side chain,
L is the mean number of the linear monomeric unit that connects.
The common degree of branching DB of branch-shape polymer is at least 99%, and especially 99.9% to 100%.
The common degree of branching DB of hyperbranched polymer is 10% to 95%, more preferably 25% to 90%, more special 30% to 80%.
For obtaining favourable freeze/thaw character, not only can utilization structure and the even branch-shape polymer of molecule, also can use hyperbranched polymer.But the preparation of hyperbranched polymer is easier so also more economical than branch-shape polymer usually.Therefore; for example; it is very complicated to prepare monodispersed branch-shape polymer; in each bonding step, to introduce and must remove blocking group once more; and before each new growth phase begins; need the high strength cleaning operation, Here it is usually only can be with the reason of bench scale preparation branch-shape polymer.Rely on its molecular weight distribution, hyperbranched polymer also can advantageously have the viscometric properties with the dispersion of its modification.In addition, hyperbranched polymer has the structure gentleer than branch-shape polymer.
Those suitable highly-branched polymer of doing that general polycondensation, addition polymerization or addition polymerization by ethylenically unsaturated compounds obtain.Preferred polycondensation product and polyaddition products.The implication of polycondensation is the repetition chemical reaction of functional compound and suitable reactive compounds, is accompanied by the elimination of low-molecular weight compound such as water, alcohol, HCl etc.The implication of addition polymerization is the repetition chemical reaction of functional compound and suitable reactive compounds, does not have the elimination of low-molecular weight compound.
What be suitable for has a polymkeric substance that comprises the functional group that preferably is selected from ether, ester group, carbonate group, amino, amide group, carbamate groups and urea groups.
As polymkeric substance, can more particularly use polycarbonate, polyester, polyethers, urethane, polyureas, polyamine and polymeric amide, with and mixed form, for example poly-(Semicarbazido manthanoate), poly-(ether amine), poly-(ester amine), poly-(ether acid amides), poly-(esteramides), poly-(amido amine), poly-(ester carbonic ether), poly-(ether carbonate), poly-(ether-ether), poly-(ether-ether carbonic ether) etc.
Preferred hyperbranched polymer has based on those of following material: ether, amine, ester, carbonic ether, acid amides, with and mixed form, for example esteramides, amido amine, ester carbonic ether, ether carbonate, ether-ether, ether-ether carbonic ether, Semicarbazido manthanoate etc.
As hyperbranched polymer, can more particularly use hyperbranched polycarbonates, hyperbranched poly (ether carbonate), hyperbranched poly (ether-ether), hyperbranched poly (ether-ether carbonic ether), hyper-branched polyester, hyperbranched polyether, super branched polyurethane, hyperbranched poly (Semicarbazido manthanoate), hyperbranched polyureas, hyperbranched polyamine, ultrabranching polyamide, hyperbranched poly (ether amine), hyperbranched poly (ester amine), hyperbranched poly (ether acid amides), hyperbranched poly (esteramides) and composition thereof.A kind of specific form of hyperbranched polymer is a hyperbranched polycarbonates.The another kind of specific form of hyperbranched polymer is the hyperbranched polymer that comprises nitrogen-atoms, especially urethane, polyureas, polymeric amide, poly-(esteramides) and poly-(ester amine).
As highly-branched polymer, preferred hyperbranched polycarbonates, poly-(ether carbonate), poly-(the ester carbonic ether) or poly-(ether-ether carbonic ether) of using perhaps comprises the mixture of the hyperbranched polymer of at least a hyperbranched polycarbonates, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether).
Hyperbranched polymer that is applicable to purposes of the present invention and preparation method thereof is recorded in the following document, and described document is included this paper in full by the mode of quoting as proof:
Height collateralization and the especially hyperbranched polycarbonates of-WO 2005/026234,
The hyper-branched polyester of-WO 01/46296, DE 10163163, DE 10219508 or DE 10240817,
The hyperbranched polyether of-WO 03/062306, WO 00/56802, DE 10211664 or DE 19947631,
The hyperbranched polymer of describing among-the WO 2006/087227 that comprises nitrogen-atoms (especially urethane, polyureas, polymeric amide, poly-(esteramides), poly-(ester amine)),
The super branched polyurethane of-WO 97/02304 or DE 19904444,
The hyperbranched poly of-WO97/02304 or DE 19904444 (Semicarbazido ethyl formate),
The hyperbranched polyureas of describing among-WO 03/066702, WO 2005/044897 and the WO 2005/075541,
Hyperbranched amido polymer, the especially polyesteramine of-WO 2005/007726,
The hyperbranched poly of-WO 99/16810 or EP 1036106 (esteramides),
The ultrabranching polyamide of describing among-the WO 2006/018125,
The hyperbranched poly of describing among-the WO 2006/089940 (ester carbonic ether).
Preferred polymkeric substance is weight average molecular weight M wAt in about 500 to 500000, preferred 750 to 200000, more special 1000 to 100000g/mol scope those.Molar mass can be determined with a standard substance such as polymethylmethacrylate by gel permeation chromatography.
In the context of the present invention, statement " alkyl " comprises straight chain and branched-chain alkyl.Suitable short-chain alkyl has for example straight or branched C 1-C 7Alkyl, preferred C 1-C 6Alkyl, more preferably C 1-C 4Alkyl.More specifically, it comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the 2-butyl, sec-butyl, the tertiary butyl, n-pentyl, the 2-amyl group, the 2-methyl butyl, the 3-methyl butyl, 1, the 2-dimethyl propyl, 1, the 1-dimethyl propyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, n-hexyl, the 2-hexyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 3-dimethylbutyl, 1, the 1-dimethylbutyl, 2, the 2-dimethylbutyl, 3, the 3-dimethylbutyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, the 1-ethyl-butyl, the 2-ethyl-butyl, 1-ethyl-2-methyl-propyl, n-heptyl, the 2-heptyl, the 3-heptyl, the 2-ethyl pentyl group, 1-propyl group butyl etc.
Suitable long-chain C 8-C 30Alkyl is the straight or branched alkyl.It preferably is mainly the straight chained alkyl type that also is present in natural or synthetic fatty acid and Fatty Alcohol(C12-C14 and C12-C18) and the oxo alcohol (oxo-process alcohol).It comprises for example n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base etc.Statement " alkyl " comprises alkyl unsubstituted and that replace.
More than also be applicable to moieties in the arylalkyl for the narration of alkyl.The preferred aryl groups alkyl is phenmethyl and styroyl.
C in the context of the invention 8-C 32Thiazolinyl is represented straight chain and branched-chain alkenyl, and it can be single, double or polyunsaturated.Preferred C 10-C 20Thiazolinyl.Statement " thiazolinyl " comprises thiazolinyl unsubstituted and that replace.Described group especially is mainly the straight-chain alkenyl type that also is present in natural or synthetic fatty acid and Fatty Alcohol(C12-C14 and C12-C18) and the oxo alcohol.More specifically, it comprises octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, inferior oil base (linolyl), flax base (linolenyl), tung oil base (eleostearyl) and oleyl (9-vaccenic acid base).
Statement on the meaning of the present invention " alkylidene group " representative contains the straight or branched alkylidene group of 1 to 7 carbon atom, as methylene radical, ethylene, trimethylene etc.
Cycloalkyl is preferably represented C 4-C 8Cycloalkyl is as cyclobutyl, cyclopentyl, cyclohexyl, suberyl or ring octyl group.
Be purpose of the present invention, it can be monocycle or Ppolynuclear aromatic hydrocarbon unsubstituted or that replace that statement " aryl " comprises.Phenyl, tolyl, xylyl, 2 are preferably represented in statement " aryl ", 4,6-trimethylphenyl, duryl (duryl), naphthyl, fluorenyl, anthryl, phenanthryl or naphthyl, more preferably represent phenyl or naphthyl, described aryl can have 1,2,3,4 or 5, preferred 1,2 or 3 substituting group usually under situation about replacing.
Being applicable to that the synthetic hyperbranched polymer that is applicable to the inventive method is more particularly is called as AB xMonomeric material.Described monomer has two different functional group A and B, and they can be reacted into key each other.Only there is a functional group A and two or more B of functional group (AB for example in the per molecule 2Or AB 3Monomer).Described AB xMonomer can be incorporated into hyperbranched polymer fully with the side chain form; They can be used as end position group incorporates into, thereby still has x free B group; They also can be used as the straight chain group with (x-1) individual free B group and incorporate into.The hyperbranched polymer that obtains has the terminal B group of more or less quantity according to the polymerization degree or as the B group of side group.Describe in further detail and see for example Journal of Molecular Science, Rev.Macromol.Chem.Phys., C37 (3), 555-579 (1997).
Except the group that in the synthesis of super branched configuration process, the forms (carbonate group under the hyperbranched polycarbonates situation for example; Carbamate groups under the super branched polyurethane situation and/or urea groups; Group with the other reaction that is derived from isocyanate group; Amide group under the ultrabranching polyamide situation etc.), the hyperbranched polymer of the present invention's use preferably comprises at least four other functional groups.The maximum number of described functional group is inessential usually.But under a lot of situations, it is no more than 100.Functional group's fragment is preferably 4 to 100, and particularly 5 to 80, more especially 6 to 50.
Other end position functional groups of the hyperbranched polymer that the present invention uses for example are independently from each other-OC (=O) OR ,-COOH ,-COOR ,-CONH 2,-CONHR ,-OH ,-NH 2,-NHR and-SO 3H.Proved end position for OH, COOH and/or-OC (=O) hyperbranched polymer of OR group is particularly advantageous.
Hyperbranched polycarbonates
Be applicable to that the hyperbranched polycarbonates that improves freeze/thaw stability can for example prepare by the following method
A) making at least a general formula is R aOC (=O) OR bOrganic carbonate (A) and at least a fatty alcohol (B) reaction that comprises at least three OH groups, eliminate pure R aOH and R bOH obtains one or more condensation products (K), R aAnd R bEach is independently from each other straight or branched alkyl, arylalkyl, cycloalkyl and aryl, R aAnd R bGroup-the OC that can also link to each other with them (=O) O-forms cyclic carbonate,
B) make described condensation product (K) intermolecular reaction obtain the hyperbranched polycarbonates of high functionality,
The ratio of OH group and carbonic ether in the choice reaction mixture is so that described condensation product (K) on average comprises or a carbonate group and an above OH group, perhaps an OH group and an above carbonate group.Radicals R aAnd R bCan have identical or different definition.In a kind of specific form, R aAnd R bHas identical definition.Preferably, R aAnd R bBe selected from C as defined above 1-C 20Alkyl, C 5-C 7Cycloalkyl, C 6-C 10Aryl and C 6-C 10Aryl-C 1-C 20Alkyl.R aAnd R bCan be C together also 2-C 6Alkylidene group.Particularly preferred R aAnd R bBe selected from straight chain and side chain C as defined above 1-C 5Alkyl.
Dialkyl group or diaryl carbonate can be---preferred single pure---with the prepared in reaction of carbonyl chloride for example by aliphatic series, araliphatic or aromatic alcohols.In addition, they also can pass through at precious metal, oxygen or NO xExistence use down the oxidative carbonylation preparation of CO to alcohol or phenol.About the preparation method of diaryl or dialkyl carbonate, also see Ullmann ' s Encyclopedia of Industrial Chemistry, the 6th edition, 2000Electronic Release, Wiley-VCH.
The example of suitable carbon acid esters comprises aliphatic series or aromatic carbonate, as ethylene carbonate, carbonic acid 1,2-propylene ester or carbonic acid 1,3-propylene ester, diphenyl carbonate, carboxylol ester, carbonic acid two (xylyl) ester, carbonic acid dinaphthyl ester, carbonic acid ethyl phenyl ester, dipheryl carbonate methyl esters, methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid diisobutyl ester, diamyl carbonate, carbonic acid dihexyl, carbonic acid two cyclohexyls, carbonic acid two heptyl esters, carbonic acid dioctyl ester, carbonic acid didecyl ester and carbonic acid two (dodecyl) ester.
The preferred aliphatic carbonate that uses, more especially wherein said group comprises those of 1 to 5 C atom, for example methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or carbonic acid diisobutyl ester.
Described organic carbonate and at least a fatty alcohol (B) reaction that comprises at least three OH groups are perhaps with the mixture reaction of two or more different alcohol.
The examples for compounds that contains at least three OH groups has glycerine, Pehanorm, trimethylolethane, TriMethylolPropane(TMP), 1,2,4-trihydroxybutane, three (hydroxymethyl) amine, three (hydroxyethyl) amine, three (hydroxypropyl) amine, tetramethylolmethane, two (TriMethylolPropane(TMP)), two (tetramethylolmethanes), Glycerol dimer, triglycerin or low Polyglycerine, sugar are as glucose, functionality is more than 3 or 3 and based on functionality to be the Aethoxy Sklerol of pure and mild oxyethane, propylene oxide or butylene oxide ring more than 3 or 3, or polyesterols.Special preferably glycerine, trimethylolethane, TriMethylolPropane(TMP), 1,2,4-trihydroxybutane, tetramethylolmethane, and based on the Aethoxy Sklerol of oxyethane or propylene oxide.
Described polyfunctional alcohol can also be using with the form of the mixture of difunctional alcohol (B '), and prerequisite is that the average OH functionality of the alcohol that all use amounts to greater than 2.The example that contains the suitable combination thing of two OH groups comprises ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol and 1, ammediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-butyleneglycol, 1,3-butyleneglycol and 1,4-butyleneglycol, 1,2-pentanediol, 1,3-pentanediol and 1,5-pentanediol, hexylene glycol, ring pentanediol, cyclohexanediol, cyclohexanedimethanol and difunctionality Aethoxy Sklerol or polyesterols.
Obtaining the reaction used high functionality hyperbranched polycarbonates of the present invention, carbonic ether and alcohol or alcohol mixture is accompanied by eliminates monofunctional alcohol or phenol from the carbonic ether molecule.
The high functionality hyperbranched polycarbonates that forms by institute's outlined approach is terminated after reaction, promptly need not with hydroxyl and/or the further modification of carbonate group.They are soluble in multiple solvent, water for example, alcohol is as methyl alcohol, ethanol, butanols, alcohol/water mixture, acetone, 2-butanone, ethyl acetate, butylacetate, acetate methoxyl group propyl ester, acetate methoxyl group ethyl ester, tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene carbonate or propylene carbonate.
The implication of high functionality polycarbonate in the context of the invention is such product, its except the carbonate group that forms polymer backbone, in the end position or ground, side position (pendently) contain at least four in addition, preferred at least eight functional groups.Described functional group is carbonate group and/or OH group.The quantity of general end position or side position functional group does not have the upper limit; But the product with high quantity functional group can show undesired character, and for example viscosity is high or poorly soluble.High functionality polycarbonate of the present invention contains usually and is no more than 500 end positions or side position functional group, preferably is no more than 100, more especially is no more than 50 end positions or side position functional group.
For preparing described high functionality polycarbonate, need to set the ratio of the compound and the carbonic ether that comprise OH, so that the simplest condensation product (condensation product (K) hereinafter referred to as) that forms on average comprises or a carbonate group and an above OH group, perhaps an OH group and an above carbonate group.The simple structure of the condensation product (K) of carbonic ether (A) and glycol or polyvalent alcohol (B) has XY nOr YX nArrangement, wherein X is a carbonate group, Y be hydroxyl and n be generally between 1 and 6, between preferred 1 and 4, the more preferably integer between 1 and 3.Reactive group--it produces with an independent group--hereinafter is commonly referred to " central group (focal group) ".
For example, when by carbonic ether and the dihydroxy alcohol the simplest condensation product of preparation (K), reaction is than being 1: 1, and average result is the molecule of the XY type of following general formula 1 explanation so.
Figure BPA00001183914400111
Under the situation with 1: 1 reaction ratio preparation condensation product (K) by carbonic ether and trihydroxy-alcohol, average result is the XY of following general formula 2 explanations 2The molecule of type.Central group is a carbonate group herein.
Figure BPA00001183914400112
When also comparing preparation condensation product (K) with 1: 1 reaction by carbonic ether and tetrahydroxy alcohol, average result is the XY of following general formula 3 explanations 3The molecule of type.Central group is a carbonate group herein.
Figure BPA00001183914400121
In formula 1 to 3, R has the implication and the R of introductory song place definition 1Be aliphatic group.
The condensation product (K) of general formula 4 explanations can also be for example by carbonic ether and the preparation of trihydroxy-alcohol, and wherein the reaction ratio in mole is 2: 1.Average result is X herein 2The molecule of Y type, wherein central group is the OH group herein.In formula 4, R and R 1Have with formula 1 to 3 in identical implication.
Figure BPA00001183914400122
---for example two carbonic ethers of glycol---when adding in the described component in addition, produces for example prolongation of the chain shown in the general formula 5 when with difunctional compound.Average result also is XY 2The molecule of type, wherein central group is a carbonate group.
Figure BPA00001183914400123
In formula 5, R 2---preferred aliphatic series---group for organic, R and R 1As above-mentioned definition.
According to the present invention, the simple condensation product of describing by way of example in formula 1 to 5 (K) carries out intermolecular reaction and forms high functionality polycondensation product (P).The reaction that obtains condensation product (K) and obtain polycondensation product (P) is body or carry out in solution under 0 to 250 ℃, preferred 60 to 160 ℃ temperature usually.In this article, can use usually various reactants are any solvent of inert.Preferably with an organic solvent, for example decane, dodecane, benzene, toluene, chlorobenzene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solvent naphtha.
In a preferred embodiment, condensation reaction is carried out with body.Simple function alcohol roh that can remove in the reaction process from molecular balance to be discharged or phenol are by the distillation mode with accelerated reaction if this removes---suitable, under reduced pressure---carry out.
Remove if be intended to distillation, generally speaking suggestion is used and emit the carbonic ether that boiling point is lower than 140 ℃ alcohol roh in reaction process.
For quickening this reaction, can also add catalyzer or catalyst mixture.Appropriate catalyst is the compound of catalytic esterification or transesterification reaction, wherein example has alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, oxyhydroxide, carbonate or the supercarbonate of preferred sodium, potassium or caesium, tertiary amine, guanidine, ammonium compound phosphonium compounds, organoaluminum, organotin, organic zinc, organic titanium, organic zirconium or bismuth organic compound, and the catalyzer that is known as double metal cyanide (DMC) catalyzer class, for example be recorded among DE 10138216 or the DE 10147712.
Preferred potassium hydroxide, salt of wormwood, the saleratus of using; diazabicyclooctane (DABCO), Diazabicyclononene (DBN), diazabicylo undecylene (DBU); imidazoles such as imidazoles, 1-Methylimidazole or 1,2 dimethylimidazole, four titanium butoxide; tetraisopropoxy titanium; Dibutyltin oxide, dibutyl tin laurate, two stannous octoates; zirconium acetylacetonate, or its mixture.
Described catalyzer in the amount of employed alcohol or alcohol mixture usually with by weight 50 to 10000ppm, preferred 100 to 5000ppm amount by weight adds.
In addition, can also be by the adding appropriate catalyst and/or by selecting suitable temperature to control described intermolecular polycondensation.In addition, the composition that the molecular-weight average of described polymkeric substance (P) can be by starting ingredient and adjust by the residence time.
At elevated temperatures Zhi Bei condensation product (K) and polycondensation product (P) usually at room temperature stable phase to the long period.
Because the character of condensation product (K), condensation reaction may produce and have different structure, has side chain but do not have crosslinked polycondensation product (P).In addition, ideal polycondensation product (P) comprises a carbonic ether central group and two above OH groups, perhaps an OH central group and two above carbonate groups.The quantity of reactive group depend on the character and the polycondensation degree of the condensation product that uses (K).
For example, the condensation product of general formula 2 (K) can form the two kinds of different polycondensation products (P) that reappear in the general formula 6 and 7 by three times of intermolecular condensation reactions.
Figure BPA00001183914400141
In formula 6 and 7, R and R 1Definition as above.
There is several different methods can stop described intermolecular polycondensation.For example, temperature can be reduced to that wherein said reaction is in halted state and product (K) or polycondensation product (P) but in the scope of stably stored.
In another embodiment, in case the intermolecular reaction of condensation product (K) obtains having the polycondensation product (P) of the polycondensation degree that needs, this reaction can stop by the product that adding in product (P) contains the group of the responding property of central group of (P).For example, under the situation of carbonic ether central group, can add for example monoamine, diamines or polyamines.Under the situation of hydroxyl central group, can in product (P), add for example monoisocyanates, vulcabond or polyisocyanates, comprise epoxide group compound or with the acid derivative of OH radical reaction.
High functionality polycarbonate of the present invention usually from 0.1 millibar to 20 crust, preferred 1 millibar to the pressure ranges of 5 crust, with in batches, prepare in the reactor of semi-batch or operate continuously or the cascade reactor.
Because above-mentioned setting reaction conditions, and if suitablely can after preparation, further process described product owing to select suitable solvent, need not other purifying.
In a further preferred embodiment, described polycarbonate not only can keep by reacting acquired functional group, also can keep other functional groups.Functionalized in the case can in the molecular weight propagation process or afterwards,---promptly after actual polycondensation finishes---carrying out.
Before molecular weight increases or in the process,, obtain having the carbonate polymer of the functional group of the random distribution that is different from carbonic ether and oh group so if add the component that also comprises other functional group or sense element except hydroxyl or carbonate group.
This type of effect can for example obtain by add following compound in polycondensation process, described compound also has other functional group or sense element except hydroxyl, carbonic ether or carbamyl cl radical, as sulfydryl, primary amino, secondary amino group or uncle's amino, ether, carboxylic acid derivative, sulfonic acid, phosphonate derivative, aryl or chain alkyl.For using the carbamate groups modification, can use for example senior alkoxylated polymerization product, 4-hydroxy piperidine, 1-hydroxyethyl piperazine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), three (hydroxymethyl) aminomethane, three (hydroxyethyl) aminomethane, quadrol, propylene diamine, hexamethylene-diamine or the isophorone diamine of thanomin, Propanolamine, Yi Bingchunan, 2-(butyl amino) ethanol, 2-(cyclohexyl amino) ethanol, 2-amino-1-butanols, 2-(2 '-amino ethoxy) ethanol or ammonia.
For with sulfhydryl modified, can use for example mercaptoethanol.Uncle's amino can be for example by introducing N methyldiethanol amine, N-methyl dipropanolamine or N, and the N-dimethylethanolamine produces.Ether can be for example is Aethoxy Sklerol generation 2 or 2 or more by introduce functionality in condensation course.Can introduce chain alkyl with the reaction of long-chain alkane glycol is feasible; Produce the polycarbonate that comprises alkyl, aryl and carbamate groups with the alkyl or aryl di-isocyanate reaction.
Subsequently functionalized can be by making formed high functionality hyperbranched polycarbonates and can reacting realization with the suitable functionalized agent of the OH of polycarbonate and/or carbonate group reaction.
Comprising the molecule that the high functionality hyperbranched polycarbonates of hydroxyl can be for example comprises acid groups or isocyanate groups by adding is modified.For example, comprising the polycarbonate of acid groups can be by obtaining with the compound reaction that comprises anhydride group.
In addition, the high functionality polycarbonate that comprises hydroxyl also can be by reaction is converted into high functionality polycarbonate-polyether glycol with epoxy alkane---for example oxyethane, propylene oxide or butylene oxide ring---.
A very big advantage of the inventive method is its economy.No matter form the reaction of condensation product (K) or polycondensation product (P), still (K) or (P) and the reaction of the formation polycarbonate of other functional groups or element all can in a reaction unit, carry out, this all is favourable technically and economically.
Hyper-branched polyester
As hyper-branched polyester, preferably use A 2B xThose of type.Particularly preferred have an A 2B 3The hyper-branched polyester of type.With AB 2The hyper-branched polyester of type is compared, described A 2B 3Polyester has the lower structure of rigidity.So AB 2The hyper-branched polyester of type is less preferred.Be applicable to that the hyper-branched polyester that improves freeze/thaw stability can be by making at least a aliphatic series, alicyclic, araliphatic or aromatic binary carboxylic acid (A 2) or derivatives thereof and following compound reaction acquisition,
A) aliphatic series of at least a trifunctional at least, alicyclic, araliphatic or aromatic alcohols (B 3), or
B) at least a divalent aliphatic, alicyclic, araliphatic or aromatic alcohols (B 2), with at least a x valency aliphatic series that comprises plural OH group, alicyclic, araliphatic or aromatic alcohols (C x), wherein x be greater than 2, preferred 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4, more especially 3 number,
Perhaps by making at least a aliphatic series that comprises two above acid groups, alicyclic, araliphatic or aromatic carboxylic acid (D y) reaction of or derivatives thereof and following compound obtains, wherein y be greater than 2, preferred 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4, more especially 3 number,
C) at least a dual functional at least aliphatic series, alicyclic, araliphatic or aromatic alcohols (B 2), or
D) at least a divalent aliphatic, alicyclic, araliphatic or aromatic alcohols (B 2), with at least a x valency aliphatic series that comprises plural OH group, alicyclic, araliphatic or aromatic alcohols (C x), wherein x be greater than 2, preferred 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4, more especially 3 number,
E) if suitable, in the presence of other functional units E and
F) randomly react with monocarboxylic acid F subsequently,
Wherein the ratio of the reactive group in the choice reaction mixture is 5: 1 to 1: 5, preferred 4: 1 to 1: 4, more preferably 3: 1 to 1: 3, extremely preferred 2: 1 to 1: 2 with the mol ratio of setting OH group and carboxyl or derivatives thereof.
The implication that is used for the hyper-branched polyester of the object of the invention is to contain hydroxyl and carboxyl and structure and the two all uneven non-crosslinked polyester of molecule.Be the purpose of this specification sheets, noncrosslinking implication is that existing degree of crosslinking that the insoluble part by polymkeric substance is determined is lower than 15 weight %, preferably is lower than 10 weight %.The insoluble part of polymkeric substance is following to be determined: extracted four hours in the Soxhlet device by using the solvent (just tetrahydrofuran (THF) or hexafluoroisopropanol--this depends on which kind of solvent has better dissolving power to described polymkeric substance) identical with solvent for use in the gel permeation chromatography, dried residue is to constant weight, and the weighing resistates.
Described di-carboxylic acid (A 2) comprise, aliphatic dicarboxylic acid for example, as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid (pimelinic acid), suberic acid, nonane diacid, sebacic acid, undecane-α, alpha, omega-dicarboxylic acid, dodecane-α, alpha, omega-dicarboxylic acid, cis-hexanaphthene-1,2-dicarboxylic acid and trans-hexanaphthene-1, the 2-dicarboxylic acid, cis-hexanaphthene-1,3-dicarboxylic acid and trans-hexanaphthene-1,3-dicarboxylic acid, cis-hexanaphthene-1,4-dicarboxylic acid and trans-hexanaphthene-1, the 4-dicarboxylic acid, cis-pentamethylene-1,2-dicarboxylic acid and trans-pentamethylene-1,2-dicarboxylic acid, cis-pentamethylene-1,3-dicarboxylic acid and trans-pentamethylene-1, the 3-dicarboxylic acid.Can also use aromatic binary carboxylic acid, for example phthalic acid, m-phthalic acid or terephthalic acid in addition.Can use unsaturated dicarboxylic acid, as toxilic acid or fumaric acid.
Described di-carboxylic acid can also be by one or more C that are selected from 1-C 10Alkyl, C 3-C 12Cycloalkyl, alkylidene group such as methylene radical or ethylidene, or C 6-C 14The group of aryl replaces.The exemplary representative of the substituted di-carboxylic acid that can mention comprises following compounds: 2-Methylpropanedioic acid, 2-ethyl malonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl succsinic acid, 2-phenyl succsinic acid, methylene-succinic acid, 3,3-dimethylated pentanedioic acid.
Can also use the mixture of two or more di-carboxylic acid of mentioning.
Described di-carboxylic acid can use with itself or with the form of its derivative.
C 1-C 4The concrete nail base of alkyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, preferable methyl, ethyl and normal-butyl, more preferably methyl and ethyl, utmost point preferable methyl.
Can also use the mixture of di-carboxylic acid and one or more its derivatives.Can use the mixture of two or more different derivatives of one or more di-carboxylic acid equally.
Especially preferably use propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, 1,2-cyclohexyl dicarboxylic acid (hexahydrophthalic acid), 1,3-cyclohexyl dicarboxylic acid (six hydrogen m-phthalic acids) or 1,4-cyclohexyl dicarboxylic acid (six hydrogen terephthalic acids), phthalic acid, m-phthalic acid, terephthalic acid or its monoalkyl or dialkyl.
Tribasic carboxylic acid that can react or polycarboxylic acid (D y) example comprise equisetic acid, 1,3,5-hexamethylene tricarboxylic acid, 1,2,4-benzene tricarbonic acid, 1,3,5-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid (1,2,4, the 5-pyromellitic acid) and mellitic acid and lower molecular weight polycarboxylic acid.
Tribasic carboxylic acid or polycarboxylic acid (D y) can use with itself or with derivative form.
Derivative is the acid anhydrides of corresponding monomer or polymerized form; Monoalkyl or dialkyl, preferred single C 1-C 4Alkyl or two C 1-C 4Alkyl ester, more preferably monomethyl or dimethyl esters or corresponding single ethyl or diethyl ester; Mono-vinyl or divinyl ester in addition; And mixed ester, preferably contain different C 1-C 4The mixed ester of alkyl component, more preferably mixed methyl ethyl ester.
Can also use the mixture of tribasic carboxylic acid or polycarboxylic acid and one or more its derivatives, for example 1,2,4, the mixture of 5-pyromellitic acid and pyromellitic dianhydride.Can use the mixture of two or more different derivatives of one or more tribasic carboxylic acids or polycarboxylic acid equally, for example 1,3, the mixture of 5-hexamethylene tricarboxylic acid and pyromellitic dianhydride.
Glycol (the B that uses 2) comprise ethylene glycol for example, the third-1, the 2-glycol, the third-1, the 3-glycol, fourth-1, the 2-glycol, fourth-1, the 3-glycol, fourth-1, the 4-glycol, fourth-2, the 3-glycol, penta-1, the 2-glycol, penta-1, the 3-glycol, penta-1, the 4-glycol, penta-1, the 5-glycol, penta-2, the 3-glycol, penta-2, the 4-glycol, oneself-1, the 2-glycol, oneself is-1 years old, the 3-glycol, oneself is-1 years old, the 4-glycol, oneself-1, the 5-glycol, oneself-1, the 6-glycol, oneself is-2 years old, the 5-glycol, heptan-1, the 2-glycol, 1, the 7-heptanediol, 1, the 8-ethohexadiol, 1, the 2-ethohexadiol, 1, the 9-nonanediol, 1, the 2-decanediol, decamethylene-glycol, 1, the 2-dodecanediol, 1, the 12-dodecanediol, 1,5-hexadiene-3,4-glycol, 1,2-encircles pentanediol and 1,3-encircles pentanediol, 1, the 2-cyclohexanediol, 1,3-cyclohexanediol and 1, the 4-cyclohexanediol, 1,1-two (hydroxymethyl) hexanaphthene, 1,2-two (hydroxymethyl) hexanaphthene, 1,3-two (hydroxymethyl) hexanaphthene and 1,4-two (hydroxymethyl) hexanaphthene, 1,1-two (hydroxyethyl) hexanaphthene, 1,2-two (hydroxyethyl) hexanaphthene, 1,3-two (hydroxyethyl) hexanaphthene and 1,4-two (hydroxyethyl) hexanaphthene, neopentyl glycol, (2)-methyl-2, the 4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1, the 3-hexylene glycol, 2,5-dimethyl-2, the 5-hexylene glycol, 2,2,4-trimethylammonium-1, the 3-pentanediol, tetramethyl ethylene ketone, glycol ether, triglycol, dipropylene glycol, tripropylene glycol, polyoxyethylene glycol HO (CH 2CH 2O) n-H or polypropylene glycol HO (CH[CH 3] CH 2O) n-H (n is integer and n 〉=4), polyethylene glycol-propylene glycol (polyethylene-polypropylene glycol, wherein the sequence of oxyethane or propylene oxide units can be a block or random), polytetramethylene glycol (preferred molar mass up to 5000g/mol), poly--1, the mixture of the representative compounds of ammediol (preferred molar mass is up to 5000g/mol), polycaprolactone or two or more compounds.One or two hydroxyls in the above-mentioned glycol can be replaced by the SH group.The preferred glycol that uses has ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,2-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-two (hydroxymethyl) hexanaphthene and 1,4-two (hydroxymethyl) hexanaphthene, glycol ether, triglycol, dipropylene glycol and tripropylene glycol, polyoxyethylene glycol HO (CH 2CH 2O) n-H or polypropylene glycol HO (CH[CH 3] CH 2O) n-H (n is integer and n 〉=4), polyethylene glycol-propylene glycol (sequence of oxyethane or propylene oxide units can be a block or random) or polytetramethylene glycol.The molecular weight of described polyalkylene glycol is preferably up to 5000g/mol.
Described dihydroxy alcohol B 2Also can randomly comprise other functional group, for example carbonyl, carboxyl, alkoxy carbonyl or alkylsulfonyl, for example dimethylol propionic acid or dimethylolpropionic acid, and C 1-C 4Alkyl ester, Zerol or glyceryl monooleate.
Functionality is at least three alcohol (C x) comprise glycerine, Pehanorm, trimethylolethane, TriMethylolPropane(TMP), 1,2, the 4-trihydroxybutane, three (hydroxymethyl) amine, three (hydroxyethyl) amine, three (hydroxypropyl) amine, tetramethylolmethane, Glycerol dimer, the senior condenses of triglycerin or glycerine, two (TriMethylolPropane(TMP)s), two (tetramethylolmethanes), isocyanuric acid trihydroxy-methyl esters, three (hydroxyethyl) isocyanuric acid ester (THEIC), three (hydroxypropyl) isocyanuric acid ester, nucite or sugar is glucose for example, fructose or sucrose, sugar alcohol such as Sorbitol Powder, N.F,USP MANNITOL, threitol (threitol), tetrahydroxybutane, adonitol (ribitol), arabitol (lyxitol), Xylitol, galactitol (melampyrum), maltose alcohol, Palatinitol (isomalt), functionality be more than 3 or 3 and be pure and mild oxyethane more than 3 or 3 based on functionality, the Aethoxy Sklerol of propylene oxide and/or butylene oxide ring.
Special herein preferably glycerine, Glycerol dimer, triglycerin, trimethylolethane, TriMethylolPropane(TMP), two (TriMethylolPropane(TMP)), 1,2,4-trihydroxybutane, tetramethylolmethane, two (tetramethylolmethane), three (hydroxyethyl) isocyanic acid urea ester and based on the Aethoxy Sklerol of oxyethane and/or propylene oxide.
This reaction can be carried out under the situation that has or do not exist solvent.The example of suitable solvent comprises hydrocarbon such as paraffin, aromatic compound, ether and ketone.Preferred this is reflected under the situation that does not have solvent and carries out.Can under the situation of reaction beginning, carry out this reaction as the existence of the water-removal agent of additive adding.Suitable example comprises that molecular sieve (especially
Figure BPA00001183914400191
Molecular sieve), MgSO 4And Na 2SO 4Can also in reaction process, pass through dephlegmate and/or alcohol, for example use water trap except that under the situation of anhydrating by azeotropic mixture.
This reaction can be carried out under the situation that does not have catalyzer.But preferably under the situation that at least a catalyzer exists, operate.Described catalyzer is preferably acid organic catalyst, organo-metallic catalyst or organic catalyst, or the mixture of two or more acid organic catalysts, organo-metallic catalyst or organic catalyst.
The acid organic catalyst that is used for the object of the invention has, for example sulfuric acid, vitriol and hydrosulfate such as sodium pyrosulfate, phosphoric acid, phosphonic acids, Hypophosporous Acid, 50, hydrazine aluminum sulfate, alum, acidic silica gel (pH≤6, especially≤5) and acidic alumina.Spendable other acid organic catalyst comprises that for example general formula is Al (OR 1) 3Aluminum compound and titanate.Preferred acid organo-metallic catalyst has, for example dialkyltin or dialkyl tin ester.Preferred acid organic catalyst has, and contains for example acidic organic compound of phosphate radical, sulfonic group, sulfate radical or phosphonate group.Acid ion exchangers also can be used as acid organic catalyst.
This is reflected under from 60 to 250 ℃ the temperature and carries out.
The molecular weight M of the hyper-branched polyester that the present invention uses wBe at least 500, preferably at least 600, more preferably 1000g/mol.Molecular weight M wThe upper limit be preferably 500000g/mol; Especially preferably be no more than 200000, extremely especially preferably be no more than 100000g/mol.
Average and the weight average molecular weight M of polydispersity and quantity nAnd M wNumerical value be meant herein and use polymethylmethacrylate to make standard substance and use tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE or hexafluoroisopropanol to make the observed value that elutriant obtains by gel permeation chromatography.This method is recorded in Analytiker Taschenbuch, the 4th volume, and 433 to 442 pages, among the Berlin 1984.
The polydispersity of the used polyester of the present invention is generally 1.2 to 50, and is preferred 1.4 to 40, and more preferably 1.5 to 30, extremely preferred 2 to 30.
Super branched polyurethane
Term used herein " urethane (polyurethane) " exceeds conventional understanding, comprise that the reaction by vulcabond or polyisocyanates and active hydrogen compounds obtains, and can be by carboxylamine ester structure and the polymkeric substance that links together of urea, allophanate, biuret, carbodiimide, acid amides, uretonimine, urea groups diketone, isocyanuric acid ester (uretdione) or oxazolidone structure for example.
The super branched polyurethane that the present invention uses can use and not only comprise isocyanate groups, also comprises the AB that can form key with the isocyanate groups reaction xMonomer is synthetic.Be the super branched polyurethane that synthetic the present invention uses, can also use to begin as intermediate formation AB xThe monomer binding substances of structure block, wherein x be between 2 and 8, preferred 2 or 3 natural number.This type of super branched polyurethane and preparation method thereof is recorded among the WO 97/02304, and this patent is included this paper in by the mode of quoting as proof.Suitable super branched polyurethane also can obtain with the reaction of the compounds of the group of responding property of isocyanic ester by making vulcabond and/or polyisocyanates and containing two at least, and wherein at least a its reactivity that comprises is different from the functional group of other reactant reactions and selective reaction condition so that the reaction each other separately of some reactive group is only arranged in the selective reaction thing in each reactions steps.This type of super branched polyurethane and preparation method thereof is recorded among the EP 1026185, and this patent is included this paper in by the mode of quoting as proof.
Described group to responding property of isocyanic ester is preferably OH-, NH 2-, NHR-or SH group.
Described AB xMonomer can prepare in a usual manner.AB xMonomer can for example use the protecting group technology synthetic by the method for describing among the WO 97/02304.This technology can be with reference to preparing AB by 2,4 toluene diisocyanate (TDI) and TriMethylolPropane(TMP) 2Monomer methods illustrates.At first, one of isocyanate groups is in a usual manner among the TDI---for example by reacting with oxime---and block.Remaining free NCO group and TriMethylolPropane(TMP) reaction, but in three OH groups one and isocyanate groups reaction are only arranged, two other OH group is by the acetalation block.Eliminate protecting group, obtain containing the molecule of an isocyanate groups and two OH groups.
A kind of particularly advantageous synthetic AB xThe method of molecule is the method for describing by among the DE-A 19904444, and base does not wherein need protection.Use vulcabond or polyisocyanates in the method, and make it and contain at least two compound reactions the group of responding property of isocyanic ester.At least a in the reactant contains the group that reactivity is different from another kind of reactant.Preferably, two kinds of reactants all contain the group that reactivity is different from another kind of reactant.Selective reaction condition by this way is so that only some reactive group can react each other.
Spendable vulcabond and polyisocyanates comprise aliphatic series well known in the prior art, alicyclic and aromatic isocyanate.Preferred vulcabond or polyisocyanates have 4, the mixture of 4 '-diphenylmethanediisocyanate, monomer diphenylmethanediisocyanate and oligomeric diphenylmethanediisocyanate (polymkeric substance MDI), tetramethylene diisocyanate, hexamethylene diisocyanate, 4, the inferior dimethyl vulcabond of 4 '-methylene radical two (cyclohexyl) vulcabond, benzene, tetramethyl for the inferior dimethyl vulcabond of benzene, dodecyl vulcabond, (wherein alkyl is C to Methionin alkyl ester vulcabond 1-C 10Alkyl), 2,2,4-trimethylammonium-1,6-hexamethylene diisocyanate or 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate, 1,4-two isocyanato hexanaphthenes or 4-isocyanato methyl isophthalic acid, 8-eight methylene diisocyanates.
The vulcabond or the polyisocyanates that especially preferably contain NCO group with differential responses, as 2,4-inferior cresyl vulcabond (2,4-TDI), 2,4 '-diphenylmethanediisocyanate (2,4 '-MDI), three isocyanato toluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethyl pentamethylene diisocyanate, 2-isocyanato propyl group cyclohexyl isocyanate, 3 (4)-isocyanato methyl isophthalic acid-isocyanatomethyl, 1,4-two isocyanatos-4-methylpentane, 2,4 '-methylene radical two (cyclohexyl) vulcabond and 4-methylcyclohexane 1,3-vulcabond (H-TDI).Particularly preferred isocyanic ester (b) in addition, the NCO group of described isocyanic ester (b) originally has equal reactivity, but can reduce in order to the reactivity that causes second NCO group when adding alcohol or amine first in the NCO group.The example has its NCO group by delocalized electron system link coupled isocyanic ester, for example 1,3-phenylene vulcabond and 1,4-phenylene vulcabond, 1,5-naphthalene diisocyanate, diphenyl diisocyanate, tolidine vulcabond or 2, the 6-inferior cresyl vulcabond.
Can also use, for example by mentioned vulcabond or polyisocyanates or low polymeric polyisocyanate or the polyisocyanates of its mixture by using following structure connection to prepare, described structure has carbamate, allophanate, urea, biuret, urea groups diketone, acid amides, isocyanic acid urea ester, carbodiimide, uretonimine, oxadiazine triketone (oxadiazinetrione) or iminooxadiazinedionepolyisocyanates diketone (iminooxadiazinedione) structure.
At least two compounds to the group of responding property of isocyanic ester that contain that use are preferably its functional group has differential responses to the NCO group two senses, trifunctional or four functional compounds.The compound that preferably contains at least one primary hydroxyl and at least one secondary hydroxyl, at least one hydroxyl and at least one sulfydryl, contain at least one hydroxyl and at least one amino compound in the preferred especially molecule, especially amino alcohol, aminodiol and amino triol are because amino reactivity with isocyanic ester is higher much than hydroxyl.
Describedly contain at least two examples for compounds propylene glycol, glycerine, mercaptoethanol, thanomin, N-Mono Methyl Ethanol Amine, diethanolamine, ethanol propanol amine, dipropanolamine, diisopropanolamine (DIPA), 2-amino-1 are arranged the group of responding property of isocyanate groups, ammediol, 2-amino-2-methyl-1, ammediol or three (hydroxymethyl) aminomethane.Also can use the mixture of mentioned compound.
AB 2The preparation of molecule can illustrate with vulcabond and aminodiol.At first one mole of vulcabond and one mole of aminodiol---preferably in from-10 to 30 ℃ the scope---are reacted at low temperatures.Under this temperature, the reaction that forms carbamate almost completely is suppressed, in the isocyanic ester reactive stronger NCO group only with aminodiol in the amino reaction.The AB that forms xMolecule contains a free NCO group and two free OH groups, can be used for synthetic height collateralization urethane.
When heating and/or adding catalyzer, this AB 2But the molecule intermolecular reaction forms height collateralization urethane.The synthetic of super branched polyurethane can advantageously be realized, need not to separate in advance in other reactions steps under the temperature (preferably in the scope between 30 and 80 ℃) that raises AB xMolecule.Use the above-mentioned AB that contains two OH groups and a NCO group 2Molecule provides per molecule to contain the hyperbranched polymer of the OH group of a free NCO group and--depending on the polymerization degree--some amount.Can carry out this react to high conversion so that the ultra high molecular weight structure to be provided.But this also can be for example by adding suitable monofunctional compound or being used to prepare AB by interpolation 2Molecule stops with one of initial compounds of reaching the desired molecule amount.According to being used for the terminated initial compounds, this reaction provides fully with the NCO end-blocking or fully with the end capped molecule of OH.
Perhaps, also can be for example by a mole of glycerin and two mole 2,4-TDI prepares AB 2Molecule.Isocyanate groups on primary alcohol group and 4 preferably at low temperatures reaction form the adducts that contains an OH group and two isocyanate groups, and as described, this adducts can be converted into super branched polyurethane under higher temperature.This reaction provides the hyperbranched polymer of the NCO group that contains a free OH group and--depending on the polymerization degree--some amount at first.
Generally speaking described super branched polyurethane can prepare under the situation without solvent, but preferably prepares in solution.Generally speaking spendable solvent comprises and at room temperature is in a liquid state and described monomer and polymkeric substance are all compounds of inert.
Other products can obtain by other synthetic deformation programs.AB for example 3Molecule can be by making vulcabond and containing at least 4 compound reaction acquisitions to the group of responding property of isocyanic ester.An example is 2, the reaction of 4-inferior cresyl vulcabond and three (hydroxymethyl) aminomethane.
This polymerization also can be used and can stop with the polyfunctional compound of various A radical reactions.This makes can be joined together to form big super branched molecule with a plurality of little super branched molecules.
The super branched polyurethane that contains the side chain of chain extension is for example can pass through AB xMolecule and other mol ratio are 1: 1 vulcabond and contain two compounds to the group of responding property of isocyanic ester and carry out polyreaction and obtain.Described other AA or BB compound also can contain other functional group, but described other functional group must not have reactivity to A or B group under the reaction conditions of selecting.This makes can introduce other functional group in described hyperbranched polymer.
The synthetic deformation program of other of super branched polyurethane is disclosed among DE 10013187 and the DE10030869.
As mentioned above, also can or change functionalization (transfunctionalize) by the functional group in the resulting super branched polyurethane of building-up reactions by hydrophobization, hydrophilization.Because its reactivity, the super branched polyurethane utmost point that comprises isocyanate groups is specially adapted to change functionalization.Can also use suitable reactive component to make OH end-blocking or NH 2End capped urethane carries out functional group's exchange.
The preferred group of introducing super branched polyurethane has-COOH ,-CONH 2,-OH ,-NH 2,-NHR ,-NR 2,-NR 3 +,-SO 3H and salt thereof.
Group with enough acid H atom can be by being converted into corresponding salt with suitable alkaline purification.Similarly, use suitable acid can make basic group be converted into corresponding salt.This makes can obtain water-soluble super branched polyurethane.
By making end capped product of NCO and alkohol and amine---especially contain C 8-C 40The alkohol and amine of alkyl---react, can obtain the product of hydrophobization.
The hydrophilization nonionic product can be by making end capped polymkeric substance of NCO and Aethoxy Sklerol---for example glycol ether, triglycol or Tetraglycol 99 or polyoxyethylene glycol---, and reaction obtains.
Acidic group can be for example by incorporating into hydroxycarboxylic acid, hydroxyl sulfoacid or amino acid whose reaction.The example of suitable reactions component has 2-oxyacetic acid, 4-hydroxy-benzoic acid, sabinic acid, 2-ethylenehydrinsulfonic acid, glycine or L-Ala.
Also can produce super branched polyurethane with different functionality.This can be for example by realizing with the reaction of the mixture of multiple compound or by functional group's---for example only a part of OH and/or NCO group---reaction that originally a part is existed.
The commentaries on classics functionalization of super branched polyurethane can advantageously carry out after polyreaction immediately, need not to separate in advance the end capped urethane of NCO.But described functionalization also can carry out in independent reaction.
The super branched polyurethane that the present invention uses on average contains at least 4 but be no more than 100 functional groups usually.Described super branched polyurethane preferably contains 8 to 80, more preferably 8 to 50 functional groups.The weight average molecular weight M of the preferred super branched polyurethane that uses WFor from 1000 to 500000g/mol, more preferably from 5000 to 200000g/mol, more especially from 10000 to 100000g/mol.
Hyperbranched polyureas
The present invention can be for example by obtaining one or more carbonic ethers and one or more amine reactions that contain at least two primary aminos and/or secondary amino group as the hyperbranched polyureas of high functionality of de-emulsifier, and wherein at least a amine contains at least three primary aminos and/or secondary amino group.
Suitable carbonic ether is aliphatic series, aromatic series or blended aliphatic series-aromatic carbonate; The preferred aliphatic series carbonic ether, as contain C 1-C 12The dialkyl carbonate of alkyl.Example has ethylene carbonate, carbonic acid 1,2-propylene ester or carbonic acid 1,3-propylene ester, diphenyl carbonate, carboxylol ester, carbonic acid dinaphthyl ester, carbonic acid ethyl phenyl ester, dipheryl carbonate methyl esters, methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid diisobutyl ester, diamyl carbonate, carbonic acid dihexyl, carbonic acid two heptyl esters, carbonic acid dioctyl ester, carbonic acid didecyl ester or carbonic acid two (dodecyl) ester.The preferred especially carbonic ether that uses has methylcarbonate, diethyl carbonate, dibutyl carbonate and carbonic acid diisobutyl ester.
Described carbonic ether and one or more contain the amine of at least two primary aminos and/or secondary amino group, at least a amine reaction that contains at least three primary aminos and/or secondary amino group.The amine that contains two primary aminos and/or secondary amino group makes chain extension in the polyureas, and the amine that contains three or more primary aminos or secondary amino group makes the hyperbranched polyureas collateralization of high functionality of formation.
Containing two has the primary amino of carbonic ether or responding property of carbamate groups or the suitable amine of secondary amino group, quadrol for example, N-alkyl quadrol, propylene diamine, 2,2-dimethyl-1, the 3-propylene diamine, N-alkyl propylene diamine, butanediamine, N-alkyl butanediamine, pentamethylene diamine, hexamethylene-diamine, N-alkyl hexamethylene-diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, the dodecane diamines, the n-Hexadecane diamines, the methylene phenylenediamine, benzene dimethylamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, inferior cyclohexanediamine, two (amino methyl) hexanaphthene, diamino diphenyl sulfone, isophorone diamine, 2-butyl-2-ethyl-1, the 5-five methylene diamine, 2,2,4-trimethylammonium-1,6-hexamethylene-diamine or 2,4,4-trimethylammonium-1, the 6-hexamethylene-diamine, 2-aminopropyl hexahydroaniline, 3 (4)-aminomethyl-1,2s-methyl cyclohexylamine, 1,4-diamino-4-methylpentane, end capped polyoxyalkylene polylol of amine (being called polyetheramine (Jeffamines)) or the end capped polytetramethylene glycol of amine.
Described amine preferably contains two primary aminos, quadrol for example, propylene diamine, 2,2-dimethyl-1, the 3-propylene diamine, butanediamine, pentamethylene diamine, hexamethylene-diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, the dodecane diamines, the n-Hexadecane diamines, tolylene diamine, the xylylene diamines, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, inferior cyclohexanediamine, diamino diphenyl sulfone, isophorone diamine, two (amino methyl) hexanaphthene, 2-butyl-2-ethyl-1, the 5-five methylene diamine, 2,2,4-trimethylammonium-1,6-hexamethylene-diamine or 2,4,4-trimethylammonium-1, the 6-hexamethylene-diamine, 2-aminopropyl hexahydroaniline, 3 (4)-aminomethyl-1,2s-methyl cyclohexylamine, 1,4-diamino-4-methylpentane, end capped polyoxyalkylene polylol of amine (being called polyetheramine) or the end capped polytetramethylene glycol of amine.
Preferred especially butanediamine, pentamethylene diamine, hexamethylene-diamine, tolylene diamine, xylylene diamines, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, inferior cyclohexanediamine, diamino diphenyl sulfone, isophorone diamine, two (amino methyl) hexanaphthene, the end capped polyoxyalkylene polylol of amine (being called polyetheramine) or the end capped polytetramethylene glycol of amine.
Containing three or more has the primary amino of carbonic ether or responding property of carbamate groups and/or the suitable amine of secondary amino group, three (amino-ethyl) amine for example, three (aminopropyl) amine, three (amino hexyl) amine, the triamino hexane, the 4-aminomethyl-1,2,8-eight methylene diamine, triaminononane, two (amino-ethyl) amine, two (aminopropyl) amine, two (amino butyl) amine, two (amino amyl group) amine, two (amino hexyl) amine, N-(2-amino-ethyl) propylene diamine, trimeric cyanamide, oligomeric diaminodiphenyl-methane, N, N '-two (3-aminopropyl) quadrol, N, N '-two (3-aminopropyl) butanediamine, N, N, N ', N '-four (3-aminopropyl) quadrol, N, N, N ', N '-four (3-aminopropyl) butanediamine, functionality is the end capped polyoxyalkylene polylol of the amine more than 3 or 3 (being called polyetheramine), functionality is the polymine more than 3 or 3, functionality is the polypropylene imines more than 3 or 3.
The amine that preferably contains three or more reactive primary aminos and/or secondary amino group has three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2, and 8-eight methylene diamine, triaminononane, two (amino-ethyl) amine, two (aminopropyl) amine, two (amino butyl) amine, two (amino amyl group) amine, two (amino hexyl) amine, N-(2-amino-ethyl) propylene diamine, trimeric cyanamide or functionality are the end capped polyoxyalkylene polylol of amine (being called polyetheramine) more than 3 or 3.
The amine that especially preferably contains three or more primary aminos, as three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2,8-eight methylene diamine, triaminononane or functionality are the end capped polyoxyalkylene polylol of the amine more than 3 or 3 (being called polyetheramine).
Will be appreciated that the mixture that also can use described amine.
Generally speaking, not only can use the amine that contains two primary aminos or secondary amino group, also can use the amine that contains three or more primary aminos or secondary amino group.This type of amine mixt can also characterize with average amine functionality, disregards nonreactive uncle's amino.So, for example diamines and triamine etc. the average functionality of molar mixture be 2.5.The amine mixt that preferably wherein average amine functionality is from 2.1 to 10---particularly from 2.1 to 5---is according to reaction of the present invention.
Be used to form the hyperbranched polyureas of the used high functionality of the present invention, carbonic ether and the reaction of diamines or polyamines be to finish by eliminating the alcohol or the phenol that are connected on the carbonic ether.If a part carbonic ether and two amino group reactions are eliminated two molecule alcohol or phenol so and are formed a urea groups.If a part carbonic ether only reacts with an amino group, eliminate a part alcohol or phenol so and form a carbamate groups.
The reaction of one or more carbonic ethers and one or more amine can be carried out in solvent.In the case, generally can use various reactants are any solvent of inert.Preferably in organic solvent, carry out described organic solvent such as decane, dodecane, benzene, toluene, chlorobenzene, dichlorobenzene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solvent naphtha.
In a preferred embodiment, this reaction is carried out with body, does not promptly add inert solvent.If alcohol that discharges in the reaction process between amine and carbonic ether or carbamate or phenol can pass through distillation---suitable, under the condition of decompression---separate, thereby it is removed from molecular balance.This also can quicken this reaction.
For quickening the reaction between amine and carbonic ether or the carbamate, also can add catalyzer or catalyst mixture.Appropriate catalyst is the compound that forms of catalytic amino manthanoate or urea normally, example has basic metal or alkaline earth metal hydroxides, basic metal or alkali metal bicarbonates, basic metal or alkaline earth metal carbonate, tertiary amine, ammonium compound, the perhaps organic compound of aluminium, tin, zinc, titanium, zirconium or bismuth.For example, can use lithium, sodium, potassium or caesium oxyhydroxide, lithium, sodium, potassium or caesium carbonate; diazabicyclooctane (DABCO), Diazabicyclononene (DBN), diazabicylo undecylene (DBU); imidazoles such as imidazoles, 1-Methylimidazole, glyoxal ethyline and 1; the 2-methylimidazole, four titanium butoxide, Dibutyltin oxide; dibutyl tin laurate; two stannous octoates, zirconium acetylacetonate, or its mixture.
Described catalyzer in the amount of used amine usually with by weight 50 to 10000ppm, preferred 100 to 5000ppm amount by weight adds.
This reaction after, modification in addition just, in this way the hyperbranched polyureas of Zhi Bei high functionality or with amino or with the carbamate groups end-blocking.They are soluble in the polar solvent, and described polar solvent has, water for example, alcohols such as methyl alcohol, ethanol, butanols, alcohol/water mixture, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene carbonate or propylene carbonate.
The hyperbranched polyureas of high functionality that is used for the object of the invention is to contain urea groups and at least four, preferred at least six, the product of at least eight functional groups particularly.Generally speaking the quantity of functional group does not have the upper limit, but the product with a myriad of functional group can show undesired character, and for example viscosity is high or poorly soluble.The high functionality polyureas that the present invention uses contains usually and is no more than 100 functional groups, preferably is no more than 30 functional groups.The implication of functional group is primary amino, secondary amino group or uncle's amino or carbamate groups herein.The hyperbranched polyureas of described in addition high functionality can comprise the other synthetic functional group (seeing below) that does not participate in described hyperbranched polymer.Described other functional group can introduce by the diamines or the polyamines that comprise other functional group except primary amino and secondary amino group.
The polyureas that the present invention uses can comprise other functional groups.In the case, functionalized can in the reaction process of carbonic ether and one or more amine, the realization---just in the polycondensation process that molecular weight increases---; Or after polycondensation finishes, carry out functionalized the realization by formed polyureas subsequently.
Before molecular weight increases or in the process, if add the component also comprise other functional group except amino or carbamate groups, product has other so---promptly being different from carbamate or the amino group---polyureas of the functional group of random distribution.
For example, before polycondensation or in the process, can add the component that except amino or carbamate groups, also comprises hydroxyl, sulfydryl, uncle's amino, ether, carboxyl, sulfonic group, phosphonate group, aryl or chain alkyl.
Comprise for carrying out the functionalized component that comprises hydroxyl that adds, for example senior alkoxylated polymerization product, 4-hydroxy piperidine, 1-hydroxyethyl piperazine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), three (hydroxymethyl) aminomethane or three (hydroxyethyl) aminomethane of thanomin, N-Mono Methyl Ethanol Amine, Propanolamine, Yi Bingchunan, butanolamine, 2-amino-1-butanols, 2-(butyl amino) ethanol, 2-(cyclohexyl amino) ethanol, 2-(2 '-amino ethoxy) ethanol or ammonia.
For the functionalized component that comprises sulfydryl that adds comprises, cysteamine for example.By uncle's amino, can functionalized described hyperbranched polyureas, by using for example N-methyl diethylenetriamine or N, N-dimethyl-ethylenediamine.By ether, can be by using the amino-terminated functionalized described hyperbranched polyureas of Aethoxy Sklerol (being called polyetheramine).By acidic group, can functionalized described hyperbranched polyureas, by using for example aminocarboxylic acid, thionamic acid or aminophosphonic acid.By chain alkyl, can contain the alkylamine or the functionalized described hyperbranched polyureas of alkyl isocyanate of chain alkyl by use.
In addition, described polyureas also can come functionalized by using the monomer that comprises the functional group that is different from amino or carbamate groups on a small quantity.Can mention by way of example that herein functionality is the alcohol more than 2,3 or 3, it can be merged in the described polyureas by carbonic ether or carbamate-functional.Therefore, for example, can obtain hydrophobic property by adding long-chain alkane glycol, enediol or alkyne diol, and make described polyureas produce hydrophilic nmature by adding polyethylene oxide glycol or triol.
Before polycondensation or the described functional group that is different from amine, carbonic ether or carbamate groups that adds in the process usually in amino, carbamate and carbonate group sum with from 0.1 to 80mol% amount, preferably add from 1 to 50mol% amount.
Can for example realize comprising the functionalized of the amino hyperbranched polyureas of high functionality subsequently: comprise the molecule of acid groups, isocyanate groups, ketone groups or aldehyde group, perhaps comprise the molecule of the two keys of activation, acrylic double bond by adding following molecule.For example, if can by with---suitable---polyureas that obtains to comprise acid groups of the reaction of vinylformic acid or toxilic acid and derivative thereof with posthydrolysis.
Can will comprise the amino hyperbranched polyureas of high functionality in addition by reaction and be converted into the high functionality polyurea polylol with oxirane---for example oxyethane, propylene oxide or butylene oxide ring---.
With protonic acid form salt or make with the quaternized amino of alkylating reagent (as methyl halide or dialkylsulfates) as described in the hyperbranched polyureas of high functionality become water soluble or water dispersible.
Be to realize hydrophobization, can make the hyperbranched polyureas of the end capped high functionality of amine and saturated or unsaturated long-chain carboxylic acid,, or react with aliphatic series or aromatic isocyanate to its derivatives reaction of responding property of amine groups.
Can be with the end capped polyureas of carbamate by reacting by hydrophobization with chain alkyl amine or long chain aliphatic monohydroxy-alcohol.
Ultrabranching polyamide
Suitable ultrabranching polyamide is by making first monomer A that contains at least two functional group A 2With second monomers B that contains at least three B of functional group 3Reaction and preparing, wherein said functional group A and B react each other, and one of described monomer is amine, and another kind of monomer is the carboxylic acid or derivatives thereof.
Suitable ultrabranching polyamide comprises ultrabranching polyamide base amine (seeing EP-A 802215, US 2003/0069370 A1 and US 2002/0161113 A1).
Although described first monomer A 2Also can contain two above functional group A, be called A herein for the sake of simplicity 2Although, and described second monomers B 3Also can contain three above B of functional group, be called B herein for the sake of simplicity 3Important factor is A in simple terms 2And B 3The functionality difference.
Described functional group A and B react each other.Select functional group A and B in the case so that A does not react (or only with unconspicuous degree reaction) with A reaction (or only with unconspicuous degree reaction) and B with B.In the case, described monomer A 2And B 3In a kind of be amine, another kind of monomer is the carboxylic acid or derivatives thereof.
Preferably, described monomer A 2For containing the carboxylic acid of at least two carboxyls, described monomers B 3For containing the amine of at least three amino.Perhaps described monomer A 2For containing the amine of at least two amino, described monomers B 3For containing the carboxylic acid of at least three carboxyls.
Suitable carboxylic acid contains 2 to 4 usually, 2 or 3 carboxyls particularly, and contains alkyl, aryl or the arylalkyl with 1 to 30 C atom.
The example of spendable di-carboxylic acid has: oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane-α, alpha, omega-dicarboxylic acid, dodecane-α, alpha, omega-dicarboxylic acid, cis-hexanaphthene-1,2-dicarboxylic acid and trans-hexanaphthene-1, the 2-dicarboxylic acid, cis-hexanaphthene-1,3-dicarboxylic acid and trans-hexanaphthene-1, the 3-dicarboxylic acid, cis-hexanaphthene-1,4-dicarboxylic acid and trans-hexanaphthene-1, the 4-dicarboxylic acid, cis-pentamethylene-1,2-dicarboxylic acid and trans-pentamethylene-1, the 2-dicarboxylic acid, and cis-pentamethylene-1,3-dicarboxylic acid and trans-pentamethylene-1, the 3-dicarboxylic acid, and di-carboxylic acid described herein can have by one or more and is selected from the replacement that following groups is carried out: C 1-C 10Alkyl, C 3-C 12Cycloalkyl, alkylidene group and C 6-C 14Aryl.The example that is substituted di-carboxylic acid that can mention has: 2-Methylpropanedioic acid, 2-ethyl malonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl succsinic acid, 2-phenyl succsinic acid, methylene-succinic acid and 3,3-dimethylated pentanedioic acid.
Other suitable compound have the ethylenic unsaturated dicarboxylic acid, as toxilic acid and fumaric acid, and aromatic binary carboxylic acid, as phthalic acid, m-phthalic acid or terephthalic acid.
The example of suitable tribasic carboxylic acid or quaternary carboxylic acid has trimesic acid, trimellitic acid, pyromellitic acid, butane tricarboxylic acid, naphthalene tricarboxylic acid and hexamethylene-1,3,5-tricarboxylic acid.
Can also use the mixture of two or more carboxylic acids of mentioning.Described carboxylic acid can use with itself or with derivative form.Described derivative in particular
The acid anhydrides of-mentioned carboxylic acid is particularly with monomer or polymerized form;
The ester of-mentioned carboxylic acid, for example
● monoalkyl or dialkyl, preferred monomethyl or dimethyl esters or corresponding single ethyl or diethyl ester, or derived from the monoalkyl or the dialkyl of higher alcohols, described higher alcohols such as n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol
● mono-vinyl or divinyl ester, and
● mixed ester, preferable methyl ethyl ester.
Can also use the mixture of forming by carboxylic acid and form by one or more its derivatives, perhaps the mixture of the different derivatives of two or more of one or more di-carboxylic acid.
More preferably the carboxylic acid of Shi Yonging comprises succsinic acid, pentanedioic acid, hexanodioic acid, cyclohexyl dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid, perhaps its monomethyl or dimethyl esters.Preferred extremely especially succsinic acid and hexanodioic acid.
Suitable amine contains 2 to 6,2 to 4 amino particularly usually, and the alkyl, aryl or the arylalkyl that contain 1 to 30 C atom.
The example of spendable diamines has formula R 1-NH-R 2-NH-R 3Those, R wherein 1, R 2And R 3Be hydrogen or alkyl, aryl or the arylalkyl that contains 1 to 20 C atom independently of one another.Described alkyl can be a straight chain, or particularly for R 2It can also be cyclic.
The example of suitable diamines has quadrol, propylene diamine (1,2-diaminopropanes and 1, the 3-diaminopropanes), the N-methyl ethylenediamine, piperazine, tetramethylene-diamine (1, the 4-diaminobutane), N, N '-dimethyl-ethylenediamine, the N-ethylethylenediamine, 1,5-diamino pentane, 1,3-diamino-2, the 2-diethyl propane, 1,3-two (methylamino) propane, hexamethylene-diamine (1), 1,5-diamino-2-methylpentane, 3-(propyl group amino) propylamine, N, N '-two (3-aminopropyl) piperazine, N, N '-two (3-aminopropyl) piperazine and isophorone diamine (IPDA).
Suitable triamine, tetramine or more the example of high functionality amine three (2-amino-ethyl) amine, three (2-aminopropyl) amine, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), inferior isopropylidene triamine, dipropylenetriamine and N are arranged, N '-two (3-aminopropyl quadrol).
Containing two or more amino amino-benzene methylamines and amino hydrazides is suitable equally.
Employed amine preferably includes DETA or three (2-amino-ethyl) amine or its mixture especially.
Can also use the mixture of two or more carboxylic acids or carboxylic acid derivative, perhaps the mixture of two or more amine.The functionality of multiple herein carboxylic acid or amine can be identical or different.
Especially, if monomer A 2Be diamines, employed monomers B 3The mixture that can comprise di-carboxylic acid and tribasic carboxylic acid (or more high functionality carboxylic acid), described mixture B 3Average functionality be at least 2.1.For example, the average functionality of the mixture that is made of 50mol% di-carboxylic acid and 50mol% tribasic carboxylic acid is 2.5.
Similarly, if monomer A 2Be di-carboxylic acid, employed monomers B 3The mixture that can comprise diamines and triamine (or more high functionality amine), described mixture B 3Average functionality be at least 2.1.This deformation program is particularly preferred.For example, the average functionality of the mixture that is made of 50mol% diamines and 50mol% triamine is 2.5.
Described monomer A 2The reactivity of middle functional group A can be identical or different.Equally, described monomers B 3The reactivity of the middle B of functional group can be identical or different.Especially, described monomer A 2In two amino or described monomers B 3In the reactivity of three amino can be identical or different.
In a preferred embodiment, carboxylic acid is two functional monomer A 2And amine is the monomers B of trifunctional 3, this is meant preferred use di-carboxylic acid and triamine or high functionality amine more.
Employed monomer A 2More preferably comprise di-carboxylic acid, employed monomers B 3More preferably comprise triamine.Employed monomer A 2The utmost point preferably includes hexanodioic acid, employed monomers B 3The utmost point preferably includes diethylenetriamine or three (2-amino-ethyl) amine.
In described monomer A 2And B 3Polymerization obtain in the process of ultrabranching polyamide or afterwards, also can use two senses or more high functionality monomer C as chain extension agent.This make can controlling polymers gelation point (form the key point of insoluble gel particle by crosslinking reaction; Referring to for example Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, the 387-398 pages or leaves) and to the modification of macromolecular structure, the i.e. connection of monomer side chain.
Therefore, present method preferred embodiment is in described monomer A 2And B 3Reaction process in or also use monomer C as chain extension agent afterwards.
The suitable example that increases chain monomer C has the above-mentioned diamines or the amine of high functionality more, thus described diamines or more amine and the different polymkeric substance side chains of high functionality carboxyl reaction and connect thereon.Specially suitable compound has isophorone diamine, quadrol, 1, the 2-diaminopropanes, 1, the 3-diaminopropanes, the N-methyl ethylenediamine, piperazine, tetramethylene-diamine (1, the 4-diaminobutane), N, N '-dimethyl-ethylenediamine, the N-ethylethylenediamine, 1,5-diamino pentane, 1,3-diamino-2, the 2-diethyl propane, 1,3-two (methylamino) propane, hexamethylene-diamine (1), 1,5-diamino-2-methylpentane, 3-(propyl group amino) propylamine, N, N '-two (3-aminopropyl) piperazine, N, N '-two (3-aminopropyl) piperazine and isophorone diamine (IPDA).
General formula is H 2The amino acid of N-R-COOH also is suitable for and makes chain extension agent C, and wherein R is an organic group herein.
The amount of described chain extension agent C depends on needed gelation point or needed macromolecular structure usually.The amount of described chain extension agent C is with the monomer A of whole uses 2And B 3Meter is generally 0.1 weight % to 50 weight %, preferred 0.5 to 40 weight %, particularly 1 weight % to 30 weight %.
For preparing functionalized polymeric amide, to follow and use simple function comonomer D, it can be in described monomer A 2And B 3Reaction before, add in the process or afterwards.This method obtains the polymkeric substance with comonomer unit and functional group's chemistry modification thereof.
Therefore, this method preferred embodiment is in described monomer A 2And B 3Reaction before, in the process or afterwards use the comonomer D that contains functional group, obtain the polymeric amide of modification.
The example of described comonomer D has saturated or unsaturated monocarboxylic acid, comprises lipid acid and acid anhydrides thereof or ester.The example of appropriate acid has acetate, propionic acid, butyric acid, valeric acid, isopropylformic acid, trimethylacetic acid, caproic acid, sad, enanthic acid, capric acid, n-nonanoic acid, lauric acid, myristic acid, palmitinic acid, montanic acid, stearic acid, Unimac 5680, n-nonanoic acid, 2 ethyl hexanoic acid, phenylformic acid, and unsaturated monocarboxylic acid (as methacrylic acid) and acid anhydrides and ester, monocarboxylic as mentioned acrylate or methacrylic ester.
The example of suitable unsaturated fatty acids D has oleic acid, ricinolic acid, linolic acid, linolenic acid, erucic acid, and the lipid acid that is derived from soybean, flaxseed, Viscotrol C and Sunflower Receptacle.
Specially suitable carboxylicesters D has methyl methacrylate, methacrylic acid hydroxyl ethyl ester and methacrylic acid hydroxyl propyl ester.
Be suitable for the alcohol that also has of making comonomer D, comprise Fatty Alcohol(C12-C14 and C12-C18).It comprises, for example glyceryl monolaurate, Zerol, ethylene glycol monomethyl ether, poly-ethylidene monomethyl ether, phenylcarbinol, 1-dodecanol, 1-tetradecanol, 1-cetyl alcohol and unsaturated fatty alcohol.
Other suitable comonomer D have acrylate, particularly alkyl acrylate such as n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, stearyl acrylate base ester, or vinylformic acid hydroxyalkyl acrylate such as Hydroxyethyl Acrylate, vinylformic acid hydroxy propyl ester and vinylformic acid hydroxyl butyl ester.Described acrylate can be introduced in the described polymkeric substance in simple especially mode by Michael addition at the amino place of ultrabranching polyamide.
The amount of described comonomer D depends on the degree of described polymer modification usually.The amount of described comonomer D is with the monomer A of whole uses 2And B 3Meter is generally 0.5 weight % to 40 weight %, preferred 1 weight % to 35 weight %.
According to the monomeric kind of use and amount and reaction conditions, described ultrabranching polyamide can contain an end position carboxyl (COOH) or the end bit amino (NH ,-NH 2), or contain the two simultaneously.For kind and quantity with the end position group of D reaction are depended in the selection of the comonomer D that carries out functionalized interpolation usually.If carboxyl terminal position group is treated modification, every mole of carboxyl terminal position group preferably uses 0.5 to 2.5, the amine of preferred 0.6 to 2, preferred especially 0.7 to 1.5 molar equivalent, for example monoamine or diamines and the triamine that particularly contains primary amino or secondary amino group.
If aminoterminal position group is treated modification, every moles of ammonia cardinal extremity position group preferably uses 0.5 to 2.5, the monocarboxylic acid of preferred 0.6 to 2, preferred especially 0.7 to 1.5 molar equivalent.
As mentioned above, Michael addition also can be used for making aminoterminal position group and mentioned acrylate reactions, for the employed acrylate molar equivalent of this purpose number is preferably every moles of ammonia cardinal extremity position group 0.5 to 2.5, particularly 0.6 to 2, more preferably 0.7 to 1.5.
Free COOH group number (acid number) in the polymeric amide end product is generally every gram polymkeric substance 0 to 400, preferred 0 to 200mg KOH, and can be for example by according to DIN 53240-2 titration determine.
Described monomer A 2Usually with described monomers B 3Reaction at elevated temperatures, for example at 80 to 180 ℃, particularly 90 to 160 ℃.Preferably at rare gas element (for example nitrogen) or under the vacuum and exist or do not exist under the situation of solvent and operate described solvent such as water, 1,4-dioxane, dimethyl formamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAC).The example of suitable solvent mixture is by water and 1, those mixtures that the 4-dioxane constitutes.But do not need to use solvent; For example carboxylic acid can be used as initial charge and is melted, and can add amine in described melt.The water of the reaction that forms in polymerization (polycondensation) process for example is drawn out of under vacuum, or uses suitable solvent (as toluene) to remove by component distillation.
Pressure is inessential usually, for example from 1 millibar to 100 the crust absolute pressures.If do not use solvent, the water of reaction can be removed with plain mode by operating down in vacuum (for example from 1 to 500 millibar).
Reaction times is generally 5 minutes to 48 hours, and preferred 30 minutes to 24 hours, more preferably 1 hour to 10 hours.
The reaction of carboxylic acid and amine can be carried out under the situation that does not have or exist catalyzer.The amidation catalyst that the example of suitable catalyst is mentioned for late phase hereinafter.
If also use catalyzer, it is measured with whole monomer A 2And B 3Meter is generally by weight 1 to 5000ppm, preferably by weight 10 to 1000ppm.
In polymerization process or afterwards, if desired, can add mentioned chain extension agent C.Be the described ultrabranching polyamide of chemical modification, also can be before polymerization process, in the process or add mentioned comonomer D afterwards.
If desired, the reaction of described comonomer D can be by conventional amidation catalyst catalysis.The example of described catalyzer has ammonium phosphate, triphenyl phosphite or dicyclohexylcarbodiimide.Particularly when using thermo-sensitivity comonomer D, with when using methacrylic ester or Fatty Alcohol(C12-C14 and C12-C18) as comonomer D, this reaction also can be by enzyme catalysis, operation usually 40 to 90 ℃, preferred 50 to 85 ℃, particularly 55 to 80 ℃ carry out down and under the situation of free radical inhibitors existence.
---and suitable for operating under rare gas element---suppresses if the radical polymerization of unsaturated functional group and undesired crosslinking reaction can be passed through inhibitor.The example of described inhibitor has quinhydrones, hydroquinone monomethyl ether, thiodiphenylamine, phenol derivatives is the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2 for example, the 4-xylenol, or N-oxycompound such as N-oxygen base-4-hydroxyl-2,2,6,6-tetramethyl piperidine (hydroxyl-TEMPO), N-oxygen base-4-oxygen-2,2,6,6-tetramethyl piperidine (TEMPO); It is based on whole monomer A 2And B 3Meter 50 to 2000ppm amount by weight uses.
This preparation preferably in batches or can carry out continuously, for example in stirred vessel, tubular reactor, tower reactor or other popular response devices, it can contain static state or dynamic mixer and be used for pressure-controlling and conventional equipment that temperature control and being used for is operated under rare gas element.
Under the situation without the solvent operation, end product directly obtains usually, and if necessary can be by conventional purification process purifying.If used solvent, can after reaction,---for example by vacuum distilling---from reaction mixture, be removed in a usual manner usually.
The characteristic of the inventive method is extremely simple.It makes can be with simple one pot reaction (one-pot reaction) preparation ultrabranching polyamide.Need not the protecting group of isolated or purified intermediate or intermediate.This method has economic advantages, because described monomer is commercially available and cheaply.
Super-branched polyesteramide
Suitable super-branched polyesteramide can be for example by preparing carboxylic acid that contains at least two carboxyls and amino alcohols reaction that contains at least one amino and at least two hydroxyls.
This method is a raw material with the carboxylic acid that contains at least two carboxyls (di-carboxylic acid, tribasic carboxylic acid or more the carboxylic acid of high functionality) with by containing at least one amino alcohol (alkanolamine) amino and that have two hydroxyls.
Suitable carboxylic acid contains 2 to 4,2 or 3 carboxyls particularly usually, and contains alkyl, aryl or the arylalkyl with 1 to 30 C atom.The carboxylic acid of being considered comprises described all di-carboxylic acid, tribasic carboxylic acid and the quaternary carboxylic acid that can be used for ultrabranching polyamide, and the derivative of described acid.
Employed carboxylic acid is succsinic acid, pentanedioic acid, hexanodioic acid, 1 more preferably, 2-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid or 1,4-cyclohexyl dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid or its dimethyl esters.Preferred extremely especially succsinic acid and hexanodioic acid.
Preferred suitable at least one amino alcohol (alkanolamine) amino and at least two hydroxyls that contain have dioxane hydramine and three alkanolamines.The example of spendable dioxane hydramine has those of formula 1
Figure BPA00001183914400361
(1)
Wherein R1, R2, R3 and R4 are hydrogen, C independently of one another 1-6Alkyl, C 3-12Cycloalkyl or C 6-14Aryl (comprising arylalkyl).
The example of suitable dioxane hydramine has diethanolamine, dipropanolamine, diisopropanolamine (DIPA), 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, two butanolamines, two isobutyl hydramine, two (2-hydroxyl-1-butyl) amine, two (2-hydroxyl-1-propyl group) amine and two hexamethylene hydramine.
Three suitable alkanolamines have those of formula 2
Figure BPA00001183914400362
(2)
Wherein R1, R2 and R3 be suc as formula 1 definition, and l, m and n are 1 to 12 integer independently of one another.For example, suitable is three (hydroxymethyl) aminomethane.
The amino alcohol that uses preferably includes diethanolamine (DEA) and diisopropanolamine (DIPA) (DIPA).
In a kind of preferred method, employed carboxylic acid comprises di-carboxylic acid, and employed amino alcohol comprises the alcohol that contains an amino and two hydroxyls.
This method also can be used for preparing functionalized polyesteramide.For this reason, also use comonomer C, and if its can be at carboxylic acid, amino alcohol before the reaction of---and proper monomer M---, add in the process or afterwards.This method obtains carrying out with comonomer unit and functional group thereof the polymkeric substance of chemical modification.
Therefore, a preferred embodiment of this method is so a kind of method, if wherein at carboxylic acid, amino alcohol before the reaction of---and proper monomer M---, in the process or also use comonomer C afterwards, obtains the polyesteramide of modification.Described comonomer can comprise one, two or more functional groups.
Suitable comonomer C has saturated and unsaturated monocarboxylic acid, before comprising at the described lipid acid of ultrabranching polyamide, its acid anhydrides and ester, alcohol, acrylate and above-mentioned simple function or more high functionality alcohol (two pure and mild polyvalent alcohols are wherein arranged), amine (diamines and triamine are wherein arranged) and amino alcohol (alkanolamine).
The amount of described comonomer C depends on the degree of polymer modification usually.The amount of described comonomer C is generally 0.5 weight % to 40 weight %, preferred 1 weight % to 35 weight % based on the whole amino alcohol and carboxylic acid meter that uses.
Free OH group's number (hydroxyl value) in the polyesteramide end product is generally every gram polymkeric substance 10 to 500, preferred 20 to 450mg KOH, and can for example determine by carrying out titration according to DIN 53240-2.
Free COOH group number (acid number) in the polyesteramide end product is generally every gram polymkeric substance 0 to 400, preferred 0 to 200mg KOH, can for example determine by carrying out titration according to DIN 53240-2 equally.
The reaction of carboxylic acid and amino alcohol is carried out usually at elevated temperatures, for example under 80 to 250 ℃, particularly under 90 to 220 ℃, under 95 to 180 ℃.If make described polymkeric substance and comonomer C reaction and use catalyzer (middle last stages sees below) for this purpose for carrying out modification, then can adjust temperature according to employed catalyzer, wherein operation usually 90 to 200 ℃, preferred 100 to 190 ℃, particularly carry out under 110 to 180 ℃.
Operation is preferably at rare gas element (for example nitrogen) or under the vacuum and exist or do not exist under the situation of solvent and carry out, described solvent for example 1,4-dioxane, dimethyl formamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAc).But do not need to use solvent; If for example carboxylic acid can mix with amino alcohol and---being suitably under the situation of catalyzer existence---reaction at elevated temperatures.The water of the reaction that forms in polymerization (polycondensation) process is for example extracted out under vacuum, or uses suitable solvent (as toluene) to remove by component distillation.
The terminal point of the reaction of carboxylic acid and amino alcohol can be increased suddenly fast by reaction mixture viscosity usually to be distinguished.When viscosity begins to increase, this reaction can for example stop by cooling.The sample of mixture can be used for determining the carboxyl number in (in advance) polymkeric substance then, for example obtains acid number according to DIN 53402-2 by titration,--suitablely--if then can add described monomer M and/or comonomer C and make its reaction.
Pressure is inessential usually, for example from 1 millibar to 100 the crust absolute pressures.If do not use solvent, the water of reaction can be by in vacuum---for example from 1 to 500 millibar absolute pressure under---, and operation is removed with plain mode.Reaction times is generally 5 minutes to 48 hours, and preferred 30 minutes to 24 hours, more preferably 1 hour to 10 hours.
As mentioned above, mentioned comonomer C can be before polymerization process, in the process or add afterwards to realize the chemical modification of super-branched polyesteramide.
This method can be used the catalyzer of the reaction (esterification) of catalysis carboxylic acid and amino alcohol.
Appropriate catalyst is an an acidic catalyst, preferred organic catalyst, organo-metallic catalyst or enzyme.
The example that can mention acid organic catalyst has sulfuric acid, phosphoric acid, phosphonic acids, Hypophosporous Acid, 50, hydrazine aluminum sulfate, alum, acidic silica gel (pH≤6, particularly≤5) and acidic alumina.It is Al (OR) that other examples of spendable acid organic catalyst have general formula 3Aluminum compound and general formula be Ti (OR) 4Titanate.The example of preferred acid organo-metallic catalyst is for being selected from dialkyltin R 2Those of SnO, wherein R as above defines.A di-n-butyl stannic oxide that especially preferably is represented as with " oxotin " commercially available acquisition of acid organo-metallic catalyst.An example of suitable material is
Figure BPA00001183914400381
The di-n-butyl stannic oxide that 4201--obtains from Atofina.
Preferred acid organic catalyst is the acidic organic compound that contains for example phosphate-based, sulfonic group, sulfate group or phosphonate group.Preferred especially sulfonic acid is as tosic acid.Can also use acid ion exchangers as acid organic catalyst, example is to comprise sulfonic group and with the polystyrene resin of the divinyl benzene crosslinked of about 2mol%.
If the use catalyzer, its amount based on whole carboxylic acids and amino alcohol meter be generally by weight 1 to 5000ppm, preferably by weight 10 to 1000ppm.
Particularly, the reaction of described comonomer C also can be by conventional amidation catalyst catalysis, usually at 40 to 90 ℃, preferred 50 to 85 ℃, particularly 55 to 80 ℃ and operate under the situation that free radical inhibitors exists.
This method can preferably be carried out in batches or continuously, for example in stirred vessel, tubular reactor, tower reactor or other popular response devices, it can contain static state or dynamic mixer and be used for pressure-controlling and conventional equipment that temperature control and being used for is operated under rare gas element.
Under the situation without the solvent operation, end product directly obtains usually, and if necessary, can be by conventional purification process purifying.If follow the use solvent, can after reaction,---for example by vacuum distilling---from reaction mixture, be removed in a usual manner.
Above-mentioned hyperbranched polymer can carry out the reaction (polymer-analogous reaction) of similar polymkeric substance in addition.In this method, can more effectively adjust its character under specific circumstances to be used for multiple dispersion.For carrying out the reaction of similar polymkeric substance, can make functional group's (for example A or the B group) reaction that originally exists in the polymkeric substance, so that the polymkeric substance that forms comprises at least a new functionality.
The reaction of the similar polymkeric substance of described hyperbranched polymer can be carried out in the polymer manufacture process, carries out immediately after polyreaction, or carries out in independent reactions steps.
Before polymkeric substance is synthetic or in the process, if the component that adds also comprises other functional group except A and B group, product is the hyperbranched polymer of the wherein said other basic random distribution of functional group so.
The compound that is used to change functionalization can comprise, at first, and the new required functional group that introduces, and second group that can form key with B radical reaction in the employed hyperbranched polymer parent material.Its a example is isocyanate groups and hydroxycarboxylic acid or forms the acid functionality with the aminocarboxylic acid reaction that perhaps the reaction of OH group and acrylic anhydride forms reactive acroleic acid pair keys.
Can use the example of the appropriate functional group of suitable reactions component introducing to comprise, particularly comprise the acidity or the basic group of H atom, and the derivative of this type of group, as-OC (O) OR ,-COOH ,-COOR ,-CONHR ,-CONH 2,-OH ,-SH ,-NH 2,-NHR ,-NR 2,-SO 3H ,-SO 3R ,-NHCOOR ,-NHCONH 2,-NHCONHR etc.If suitable, also can use suitable acid or alkali that ionizable functional group is converted into corresponding salt.Another kind for example may be to use alkyl halide or dialkylsulfates to carry out quaternized to primary amino, secondary amino group or uncle's amino.This method can be used for for example obtaining water-soluble or the water dispersible hyperbranched polymer.
R base in the described group is preferably straight or branched, the unsubstituted or alkyl that replaces.For example, it is C 1-C 30Alkyl or C 6-C 14Aryl.The example of appropriate functional group has-CN or-OR a, R wherein a=H or alkyl.
For use hyperbranched polymer in dispersion, it is favourable that hydrophilic and hydrophobic part has specified proportion each other.The hydrophobization of hyperbranched polymer can be for example by using the simple function hydrophobic compound finish, wherein with described simple function hydrophobic compound before polymerization, in the process or the reactive group of the existence of modification afterwards.Therefore, for example, polymkeric substance of the present invention can be by the reaction of or unsaturated aliphatic or aromatic amine, alcohol, carboxylic acid, epoxide or isocyanic ester saturated with simple function by hydrophobization.
In addition, can also for example introduce two senses or the higher functional monomer who comprises hydrophobic grouping by copolymerization in the molecular weight propagation process.For this purpose, can for example use two senses or higher functional alcohol, amine, isocyanic ester, carboxylic acid and/or epoxide, it also has aromatic group or chain alkyl, alkenyl or alkynyl (akyne radical) except reactive group.
This type of monomeric example has alcohol, as Zerol, glyceryl monooleate, hexylene glycol, ethohexadiol, decanediol, dodecanediol, octadecandiol, dimerization Fatty Alcohol(C12-C14 and C12-C18); Amine is as hexamethylene-diamine, octamethylenediamine, dodecane diamines; Isocyanic ester, as aromatic series or aliphatic vulcabond or polyisocyanates, for example diphenylmethanediisocyanate and higher oligopolymer material, tolylene diisocyanate, naphthylidene two isocyanic acids, xylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, two (two isocyanato cyclohexyl) methane or two (isocyanato methyl) hexanaphthene thereof; And acid, as hexanodioic acid, suberic acid, dodecanedioic acid, octadecane diacid or dimer (fatty acid) yl.
The hyperbranched polymer that the present invention uses also can be by hydrophilization.This hyperbranched polymer that can be for example will comprise hydroxyl and/or primary amino or secondary amino group by the reaction with oxirane---as oxyethane, propylene oxide, butylene oxide ring or its mixture---is converted into the high functionality polymer polyatomic alcohol to carry out.For carrying out alkoxylate, preferably use oxyethane.But select as another kind of, functionality is that epoxy alkanol or the epoxy alkanamine more than 2 or 2 can be used as synthetic component in preparation hyperbranched polymer process.
Also can produce hyperbranched polymer with different functionality.This can be for example by finishing with the mixture reaction of the different compounds that are used to change functionalization, or finish by the functional group reactions that originally a part is existed.
Also can be used for polymeric ABC or AB by use 2The monomer of C type produces the compound with mixed functionality, wherein the C representative under the reaction conditions of selecting not with the functional group of A or B reaction.
Polymeric dispersions PD
Polymeric dispersions PD) uses at least a ethylenically unsaturated monomers (M) preparation.Described monomer (M) comprises α, and β-ethylenically unsaturated monomers is purpose of the present invention, and described α, β-ethylenically unsaturated monomers are interpreted as containing the monomer of the two keys in end position.Described monomer (M) preferably is selected from α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 1-C 20The ester of alkanol, vinyl aromatic compound, vinyl alcohol and C 1-C 30Monocarboxylic ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide, single ethylenic unsaturated carboxylic acid and sulfonic acid, phosphorus monomer, α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 2-C 30The ester of alkane glycol, α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and comprise primary amino or the C of secondary amino group 2-C 30The acid amides of amino alcohol, α, β-ethylenic unsaturated monocarboxylic acid and N-alkyl and N, the primary amide of N-dialkyl derivatives, N-vinyl lactam, open chain N-vinylamide compound, allyl alcohol and C 1-C 30Monocarboxylic ester, α, ester, the α of β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and amino alcohol, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and comprise acid amides, the N of the diamines of at least one primary amino or secondary amino group, N-diallyl amine, N, nitrogen heterocyclic, vinyl ether, C that N-diallyl-N-alkylamine, vinyl and allyl group replace 2-C 8Monoolefine, the non-aromatic hydrocarbon that contains at least two conjugated double bonds, polyethers (methyl) acrylate, comprise the monomer of urea groups, and composition thereof.
Suitable α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 1-C 20The ester of alkanol has (methyl) methyl acrylate, ethylacrylic acid methyl esters (methyl ethacrylate), (methyl) ethyl propenoate, the ethyl propylene acetoacetic ester, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, the ethyl propylene tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid 1,1,3,3-tetramethyl-butyl ester, (methyl) EHA, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid n-undecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid cardamom ester, (methyl) vinylformic acid pentadecane ester, (methyl) vinylformic acid palm ester, (methyl) vinylformic acid heptadecane ester, (methyl) vinylformic acid nonadecane ester, (methyl) vinylformic acid peanut ester, (methyl) vinylformic acid Shan Yu ester, (methyl) vinylformic acid tetracosane ester, (methyl) vinylformic acid hexacosane ester (cerotinyl (meth) acrylate), (methyl) vinylformic acid triacontane ester (melissinyl (meth) acrylate), (methyl) vinylformic acid palmityl ester (palmitoleyl (meth) acrylate), (methyl) vinylformic acid oil alkene ester, the inferior grease of (methyl) vinylformic acid, (methyl) vinylformic acid linaethol, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, and composition thereof.
Preferred vinyl aromatic compound has vinylbenzene, 2-methyl styrene, 4-vinyl toluene, 2-(normal-butyl) vinylbenzene, 4-(normal-butyl) vinylbenzene, 4-(positive decyl) vinylbenzene, special optimization styrene.
Suitable vinyl alcohol and C 1-C 30Monocarboxylic ester has, for example vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester, propionate, tertiary monocarboxylic acid (versatic acid) vinyl acetate, and composition thereof.
Suitable ethylenic unsaturated nitrile has vinyl cyanide, methacrylonitrile, and composition thereof.
Suitable vinyl halide and vinylidene halide have vinylchlorid, Ethylene Dichloride, vinyl fluoride, difluoroethylene, and composition thereof.
Suitable ethylenic unsaturated carboxylic acid and sulfonic acid or derivatives thereof have vinylformic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan, butenoic acid, toxilic acid, maleic anhydride, methylene-succinic acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid, equisetic acid, fumaric acid, the monoesters monomethyl maleate for example that contains single ethylenic unsaturated dicarboxylic acid of 4 to 10 and preferred 4 to 6 C atoms, vinyl sulfonic acid, allyl sulphonic acid, vinylformic acid sulphur ethyl ester, methacrylic acid sulphur ethyl ester, vinylformic acid sulphur propyl ester, methacrylic acid sulphur propyl ester, 2-hydroxyl-3-acryloyl-oxy propanesulfonic acid, 2-hydroxy-3-methyl acryloyl-oxy propanesulfonic acid, styrene sulfonic acid and 2-acrylamido-2-methyl propane sulfonic acid.Suitable styrene sulfonic acid and derivative thereof have vinylbenzene-4-sulfonic acid and vinylbenzene-3-sulfonic acid and basic metal or alkaline earth salt, for example vinylbenzene-3-sodium sulfonate and vinylbenzene-4-sodium sulfonate.Preferred especially vinylformic acid, methacrylic acid and composition thereof.
The monomeric example of phosphorus has for example vinyl phosphonate and allyl group phosphonic acids.Suitable monoesters or the diester, the especially monoesters that also have phosphonic acids and phosphoric acid and (methyl) vinylformic acid hydroxyalkyl acrylate.Suitable in addition having use the esterification of (methyl) vinylformic acid hydroxyalkyl acrylate cross once with cross with (for example alkanol) esterifications of different alcohol once phosphonic acids and the diester of phosphoric acid.To suitable (methyl) vinylformic acid hydroxyalkyl acrylate of described ester have the independent monomer of following conduct indicated those, more especially (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester etc.Corresponding dihydrogen phosphate monomer comprises (methyl) vinylformic acid phosphorus alkyl ester, as (methyl) vinylformic acid 2-phosphorus ethyl ester, (methyl) vinylformic acid 2-phosphorus propyl ester, (methyl) vinylformic acid 3-phosphorus propyl ester, (methyl) vinylformic acid phosphorus butyl ester and (methyl) vinylformic acid 3-phosphorus-2-hydroxy propyl ester.The suitable ester that also has phosphonic acids and phosphoric acid and oxyalkylated (methyl) vinylformic acid hydroxyalkyl acrylate, example has (methyl) acrylic acid ethylene oxide condensate, as H 2C=C (H, CH 3) COO (CH 2CH 2O) nP (OH) 2And H 2C=C (H, CH 3) COO (CH 2CH 2O) nP (=O) (OH) 2, wherein n is 1 to 50.Suitable butenoic acid phosphorus alkyl ester, toxilic acid phosphorus alkyl ester, fumaric acid phosphorus alkyl ester, (methyl) vinylformic acid phosphorus dialkyl, butenoic acid phosphorus dialkyl and phosphoric acid allyl ester in addition.The suitable in addition monomer that comprises the phosphorus group is recorded among WO 99/25780 and the US 4,733,005, and described patent is included this paper in by the mode of quoting as proof.
Suitable α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 2-C 30The ester of alkane glycol has, for example vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, ethylacrylic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, vinylformic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, vinylformic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, the own ester of vinylformic acid 6-hydroxyl, the own ester of methacrylic acid 6-hydroxyl, vinylformic acid 3-hydroxyl-2-ethylhexyl, methacrylic acid 3-hydroxyl-2-ethylhexyl etc.
Suitable α; β-ethylenic unsaturated monocarboxylic acid and N-alkyl and N; the primary amide of N-dialkyl derivatives has acrylamide; Methacrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tertiary butyl (methyl) acrylamide; N-n-octyl (methyl) acrylamide; N-(1; 1; 3; the 3-tetramethyl butyl) (methyl) acrylamide; N-ethylhexyl (methyl) acrylamide; N-n-nonyl (methyl) acrylamide; the positive decyl of N-(methyl) acrylamide; N-n-undecane base (methyl) acrylamide; N-tridecyl (methyl) acrylamide; N-myristyl (methyl) acrylamide; N-pentadecyl (methyl) acrylamide; N-palmityl (methyl) acrylamide; N-heptadecyl (methyl) acrylamide; N-nonadecyl (methyl) acrylamide; N-Semen arachidis hypogaeae base (methyl) acrylamide (N-araquinyl (meth) acrylamide); N-Shan Yu base (methyl) acrylamide; N-tetracosyl (methyl) acrylamide; N-ceryl (methyl) acrylamide (N-cerotinyl (meth) acrylamide); N-hexatriacontane base (methyl) acrylamide (N-melissinyl (meth) acrylamide); N-palmitoyl (methyl) acrylamide (N-palmitoleyl (meth) acrylamide); N-oil base (methyl) acrylamide; inferior oil base (methyl) acrylamide of N-; N-flax base (methyl) acrylamide; N-stearyl (methyl) acrylamide; N-lauryl (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N, N-diethyl (methyl) acrylamide; morpholinyl (methyl) acrylamide.
Suitable N-vinyl lactam and derivative thereof have, for example N-vinyl pyrrolidone, N-vinyl piperidone, N-caprolactam, N-vinyl-5-N-methyl-2-2-pyrrolidone N-, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-hexanolactam, N-vinyl-7-ethyl-2-hexanolactam etc.
Suitable open chain N-vinylamide compound has, for example N-vinyl formamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl propionic acid amide, N-vinyl-N-methyl propanamide and N-vinyl butyramide.
Suitable α, the ester of β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and amino alcohol has N, N-dimethylaminomethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl propylene acid esters, N, N-dimethylaminopropyl (methyl) acrylate, N, N-diethylamino propyl group (methyl) acrylate and N, N-dimethylamino cyclohexyl (methyl) acrylate.
Suitable α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and the acid amides that comprises the diamines of at least one primary amino or secondary amino group have N-[2-(dimethylamino) ethyl] acrylamide, N-[2-(dimethylamino) ethyl] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[4-(dimethylamino) butyl] acrylamide, N-[4-(dimethylamino)-butyl] Methacrylamide, N-[2-(diethylamino) ethyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] Methacrylamide etc.
In addition, suitable monomers M) N is arranged, N-diallyl amine and N, N-diallyl-N-alkylamine and acid salt and quaternized products.The preferred C of alkyl herein 1-C 24Alkyl.Preferred N, N-diallyl-N-methylamine and N, N-diallyl-N, N-Dimethyl Ammonium compound, for example muriate and bromide.
Other suitable monomers M) also has by the nitrogen heterocyclic of vinyl and allyl group replacement, as N-vinyl imidazole, N-vinyl-glyoxal ethyline, and by the heteroaromatic compound of vinyl and allyl group replacement, as 2-vinyl pyridine and 4-vinylpridine, 2-allyl pyridine and 4-allyl pyridine, and salt.
The appropriate C that contains at least two conjugated double bonds 2-C 8Monoolefine and non-aromatic hydrocarbon have ethene, propylene, iso-butylene, isoprene, divinyl etc.
Suitable polyethers (methyl) acrylate has the compound of following general formula (A)
(A)
Wherein
The order of epoxy alkane unit is random,
K and l are from 0 to 100 integer independently of one another, and k and l sum minimum are 3,
R aBe hydrogen, C 1-C 30Alkyl, C 5-C 8Cycloalkyl, C 6-C 14Aryl or (C 6-C 14) aryl-(C 1-C 4) alkyl,
R bBe hydrogen or C 1-C 8Alkyl,
Y is O or NR c, R wherein cBe hydrogen, C 1-C 30Alkyl or C 5-C 8Cycloalkyl.
Preferably k is from 1 to 100, more preferably 3 to 50, and 4 to 25 integer more especially.Preferably l is from 0 to 100, more preferably 3 to 50, and 4 to 25 integer more especially.
K and l sum are preferably from 3 to 200, and more especially 4 to 100.
The R in the formula (A) preferably aBe hydrogen or C 1-C 18Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl and phenmethyl.
R preferably bBe hydrogen or C 1-C 6Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl or n-hexyl, more especially hydrogen, methyl or ethyl.Preferred especially R bBe hydrogen or methyl.
Preferably the Y in the formula (A) is O or NH, especially O.
In a concrete scheme, at least a polyethers (methyl) acrylate is used for free-radical emulsion polymerization with preparation PD).This polyethers (methyl) acrylate is based on described monomer M) the gross weight meter preferably with up to 25 weight %, more preferably use up to the amount of 20 weight %.This letex polymerization more preferably uses at least a polyethers (methyl) acrylate of 0.1 weight % to 20 weight %, preferred 1 weight % to 15 weight % to carry out.The example of suitable polyethers (methyl) acrylate has above-mentioned α, the polycondensation product of β-ethylenic unsaturated monocarboxylic acid and/or di-carboxylic acid and chloride of acid thereof (acid chloride), acid amides (acid amide) and acid anhydrides and Aethoxy Sklerol.Suitable Aethoxy Sklerol is easy to by oxyethane, 1,2 epoxy prapane and/or Epicholorohydrin and a kind of starting molecule (as water or short chain alcohol R a-OH) prepared in reaction.Oxirane can perhaps alternately use individually in succession or with form of mixtures.Polyether acrylate can be used to prepare the emulsion polymer that the present invention uses separately or with form of mixtures.
Described polymeric dispersions PD) preferably comprises at least a polyethers (methyl) acrylate that is selected from the compound of general formula I or II or its mixture of copolymerized form
Wherein
N is from 3 to 15, preferred 4 to 12 integer,
R aBe hydrogen, C 1-C 20Alkyl, C 5-C 8Cycloalkyl or C 6-C 14Aryl,
R bBe hydrogen or methyl.
Suitable polyethers (methyl) acrylate is commercially available, for example to be called
Figure BPA00001183914400462
The form of multiple product from Laporte Performance Chemicals, the commercially available acquisition of UK.It for example comprises
Figure BPA00001183914400463
MPEG 350MA--methoxy poly (ethylene glycol) monomethacrylates.
In another concrete scheme, describedly be used to prepare PD) free-radical emulsion polymerization use at least a monomer that comprises urea groups to carry out.This monomer is based on described monomer M) the gross weight meter preferably with up to 25 weight %, preferably use up to the amount of 20 weight %.Preferred especially described letex polymerization is to use 0.1 weight % to 20 weight %, more especially at least a monomer that comprises urea groups of 1 to 15 weight % carries out.The suitable monomeric example that comprises urea groups has the derivative of N-vinyl urea or N-allyl urea or tetrahydroglyoxaline-2-ketone.It comprises N-vinyl imidazole quinoline-2-ketone and N-allyl imidazole quinoline-2-ketone, N-vinyl oxygen ethyl imidazol(e) quinoline-2-ketone, N-(2-(methyl) acrylamide ethyl) tetrahydroglyoxaline-2-ketone, N-(2-(methyl) acrylyl oxy-ethyl) tetrahydroglyoxaline-2-ketone (being 2-urea groups (methyl) acrylate), N-[2-((methyl) acryloyl-oxy acetamido) ethyl] tetrahydroglyoxaline-2-ketone etc.
The monomer that preferably comprises urea groups has N-(2-acrylyl oxy-ethyl) tetrahydroglyoxaline-2-ketone and N-(2-methylacryoyloxyethyl) tetrahydroglyoxaline-2-ketone.Preferred especially N-(2-methylacryoyloxyethyl) tetrahydroglyoxaline-2-ketone (2-urea groups methacrylic ester, UMA).
Above-mentioned monomer M) can be individually, with the monomeric form of mixtures of a class or to use with the monomeric form of mixtures of inhomogeneity.
Be letex polymerization, preferably use based on described monomer M) gross weight meter at least 40 weight %, more preferably at least 60 weight %, at least a following monomer M 1 that is selected from of at least 80 weight % more especially): α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 1-C 20The ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30Monocarboxylic ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide and composition thereof (principal monomer).Preferred described monomer M 1) based on described monomer M) the gross weight meter with up to 99.9 weight %, more preferably up to 99.5 weight %, more especially the amount up to 99 weight % is used for letex polymerization.
Principal monomer M1) is preferably selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, the just own ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, vinylbenzene, 2-methyl styrene, vinyl-acetic ester, vinyl cyanide, methacrylonitrile and composition thereof.
Except at least a principal monomer M1), be used for preparing PD) free-radical emulsion polymerization also can use at least a usually a small amount of other monomer M 2 that exists) (second monomer).For carrying out letex polymerization, preferably use based on described monomer M) the gross weight meter up to 60 weight %, more preferably up to 40 weight %, more especially up at least a following monomer M 2 that is selected from of 20 weight %): the acid anhydrides of ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and ethylenic unsaturated dicarboxylic acid and monoesters, ethylenic unsaturated sulfonic acid, (methyl) acrylamide, C 1-C 10Hydroxyalkyl (methyl) acrylate, C 1-C 10Hydroxyalkyl (methyl) acrylamide and composition thereof.If exist, preferred described monomer M 2) based on described monomer M) the gross weight meter with at least 0.01 weight %, more preferably at least 0.05 weight %, more especially at least 0.1 weight %, especially at least 0.5 weight %, more particularly the amount of at least 1 weight % is used for letex polymerization.
For carrying out letex polymerization, especially preferably use 0.1 weight % to 60 weight %, preferred 0.5 weight % to 40 weight %, at least a monomer M 2 of 0.1 weight % to 20 weight % more especially).In first kind of deformation program, described monomer M 2) comprise at least a monomer that has acid groups, described monomer is preferably selected from the unsaturated C of single ethylenic 3-C 8Monocarboxylic acid, the unsaturated C of single ethylenic 4-C 8Di-carboxylic acid, its acid anhydrides and monoesters, single ethylenic unsaturated sulfonic acid and composition thereof.The monomer M 2 that has acid groups) partly (if exist) is based on described monomer M) the gross weight meter be preferably 0.05 weight % to 15 weight %, more preferably 0.1 weight % to 10 weight %.In second kind of deformation program, described monomer M 2) comprises at least a unsaturated C of single ethylenic that is preferably selected from 3-C 8Monocarboxylic acid amides, the unsaturated C of single ethylenic 3-C 8Monocarboxylic hydroxyl-C 2-C 4Alkyl ester, and composition thereof neutral single ethylenically unsaturated monomers.Described neutral monomer M2) partly (if exist) is based on described monomer M) the gross weight meter be preferably 0.01 weight % to 15 weight %, more preferably 0.1 weight % to 10 weight %.In the third deformation program, described monomer M 2) comprises at least a monomer of acid groups and the mixture of the single ethylenically unsaturated monomers of at least a neutrality of having.Described monomer M 2) summation is based on described monomer M) the gross weight meter be preferably 0.1 weight % to 20 weight %, more preferably 0.5 weight % to 15 weight %.Described monomer M 2) especially is selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, maleic anhydride, acrylamide, Methacrylamide, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl Methacrylamide and composition thereof.
The principal monomer M1 that is used for the inventive method) specially suitable monomer bonded example is as follows:
N-butyl acrylate, methyl methacrylate;
N-butyl acrylate, vinylbenzene;
N-butyl acrylate, methyl methacrylate, vinylbenzene;
N-butyl acrylate, EHA, methyl methacrylate;
N-butyl acrylate, EHA, vinylbenzene;
EHA, vinylbenzene;
EHA, methyl methacrylate;
EHA, methyl methacrylate, vinylbenzene.
Above-mentioned specially suitable principal monomer M1) binding substances can with specially suitable monomer M 2) combine described monomer M 2) be preferably selected from vinylformic acid, methacrylic acid, acrylamide, Methacrylamide and composition thereof.
In the preparation of polymeric dispersions of the present invention, except above-mentioned monomer M) can use at least a linking agent.Monomer with crosslinked function is the compound that contains at least two unsaturated unconjugated double bonds of polymerisable ethylenic in the molecule.Crosslinkedly also can for example be undertaken by photochemical activation.For this purpose, but can use at least a monomer that comprises the photoactivation group to prepare PD in addition).Also can add photoinitiator separately.Crosslinked also can for example the use can be given the functional group that chemical crosslink reaction replenishes functional group and finished.In the case, described additional group all can be connected to emulsion polymer with crosslinked, can use the functional group that can make described emulsion polymer that the linking agent of chemical crosslink reaction takes place.
Suitable crosslinking agent has, for example the acrylate of dibasic alcohol, methacrylic ester, allyl ethers or vinyl ether at least.The OH group of parent alcohol can be by all or part of etherificate or esterification; But linking agent comprises at least two ethylenic unsaturated groups.
The example of parent alcohol has dibasic alcohol such as 1,1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1,3 butylene glycol, 2, the 3-butyleneglycol, 1, the 4-butyleneglycol, but-2-ene-1, the 4-glycol, 1, the 2-pentanediol, 1, the 5-pentanediol, 1, the 2-hexylene glycol, 1, the 6-hexylene glycol, decamethylene-glycol, 1, the 2-dodecanediol, 1, the 12-dodecanediol, neopentyl glycol, 3-methylpent-1, the 5-glycol, 2,5-dimethyl-1,3-hexylene glycol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 2-cyclohexanediol, 1, the 4-cyclohexanediol, 1,4-two (hydroxymethyl) hexanaphthene, hydroxy new pentane acid neopentyl glycol monoesters, 2,2-two (4-hydroxy phenyl) propane, 2,2-two [4-(2-hydroxypropyl) phenyl] propane, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, four propylene glycol, 3-sulfo-pentane-1,5-glycol, and respectively do for oneself 200 to 10000 polyoxyethylene glycol of molecular weight, polypropylene glycol and polytetrahydrofuran.Except the homopolymer of oxyethane or propylene oxide, also can use the segmented copolymer of oxyethane or propylene oxide, or comprise the multipolymer of oxyethane and propylene oxide group.The example that contains the parent alcohol of two above OH groups has TriMethylolPropane(TMP), glycerine, tetramethylolmethane, 1,2,5-penta triol, 1,2, and 6-hexanetriol, tricyanic acid, sorbitanic, sugar are as sucrose, glucose and seminose.Certainly, described polyvalent alcohol also can with the reaction of oxyethane or propylene oxide after use with corresponding ethoxylate or propoxylated glycerine form.Described polyvalent alcohol also can be at first by being converted into corresponding glycidyl ether with the Epicholorohydrin reaction.
Suitable crosslinking agent has vinyl ester or monobasic unsaturated alcohol and the unsaturated C of ethylenic in addition 3-C 6The ester of carboxylic acid, the unsaturated C of described ethylenic 3-C 6The example of carboxylic acid has vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or fumaric acid.This type of pure example has allyl alcohol, 1-butylene-3-alcohol, 5-hexen-1-ol, 1-octene-3-alcohol, 9-decen-1-ol, two cyclopentenols, 10-undecene-1-alcohol, styryl carbinol, geraniol, crotyl alcohol or suitable-9-vaccenic acid-1-alcohol.The another kind of selection is with polycarboxylic acid the monobasic unsaturated alcohol to be carried out esterification, and the example of described polycarboxylic acid is propanedioic acid, tartrate, 1,2,4-benzenetricarboxylic acid, phthalic acid, terephthalic acid, citric acid or succsinic acid.
Other suitable crosslinking agent have the ester of unsaturated carboxylic acid and above-mentioned polyvalent alcohol, and example is the ester of oleic acid, Ba Dousuan, styracin or 10-undecylenic acid.
Suitable crosslinking agent has straight or branched, linearity or ring-type, aliphatic series or the aromatic hydrocarbons that contains at least two two keys in addition, under the situation of aliphatic hydrocrbon, described at least two two keys are conjugation not, example has Vinylstyrene, divinyl toluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-tetrahydrobenzene, trivinyl hexanaphthene or molecular weight are 200 to 20000 polyhutadiene.
Suitable crosslinking agent has the N-allyl amine of acrylamide, Methacrylamide and at least two functional amine in addition.This type of amine has, 1,1 for example, 3-diaminopropanes, 1,4-diaminobutane, 1,1,12-dodecane diamines, piperazine, diethylenetriamine or isophorone diamine.The suitable acid amides that forms by allyl amine and unsaturated carboxylic acid in addition, described unsaturated carboxylic acid such as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, or the di-carboxylic acid at least of mentioned kind.
In addition, triallylamine and triallyl monoalkyl ammonium salt---for example triallyl ammonio methacrylate or triallyl methyl ammonium sulfate---are suitable for makes linking agent.
The suitable N-vinyl compound that also has urea derivatives, at least two functional acid amides, cyanurate or carbamate, the N-vinyl compound of urea, ethylidene-urea, propylidene urea or tartramide for example, as N, N '-divinyl ethylidene-urea or N, the N-vinyl compound of N '-divinyl propylidene urea.
Suitable crosslinking agent has divinyl dioxane, tetraallyl silane or tetrem thiazolinyl silane in addition.
Will be appreciated that the mixture that also can use above-claimed cpd.The preferred water-soluble cross-linker that uses.
Cross-linking monomer comprises that also those also comprise the monomer of the reactive functional groups that can react with the linking agent of interpolation, described reactive functional groups such as aldehyde radical, ketone group or Oxyranyle except the ethylenic unsaturated double-bond.Described functional group is preferably ketone group or aldehyde radical.But described ketone group or the aldehyde radical preferably copolymerization of the copolymerization ethylenically unsaturated compounds by having ketone group or aldehyde radical are connected on the polymkeric substance.This suitable compounds has propenal; Methylacrylaldehyde; contain 1 to 20, the vinyl alkyl ketone of preferred 1 to 10 carbon atom in the alkyl; formyl radical vinylbenzene; (methyl) alkyl acrylate that contains one or two ketone group or aldehyde radical or an aldehyde radical and a ketone group in the alkyl; described alkyl preferably comprises 3 to 10 carbon atoms altogether, and example is (methyl) acryloyloxyalkyl propionic aldehyde, as describing among the DE-A-2722097.Suitable in addition also have for example known N-oxyalkyl (methyl) acrylic amide from US-A-4226007, DE-A-2061213 or DE-A-2207209.Particularly preferred is acetoacetyl (methyl) acrylate, acetoacetyl oxygen ethyl (methyl) acrylate, more particularly diacetone-acryloamide(DAA).Described linking agent is preferably and contains at least 2 functional groups, the compound of 2 to 5 functional groups more especially, and it can make the functional group of described polymkeric substance---especially ketone group or aldehyde radical---, and crosslinking reaction takes place.The functional group that is used for crosslinked ketone group or aldehyde radical comprises, for example hydrazides, oxyamine or oxime ether or amino group.The compound of suitable hydrazides group has, and for example molar weight is up to the polynary carboxylic hydrazides of 500g/mol.Particularly preferred hydrazide compound has binary carboxyl two hydrazides that preferably contain 2 to 10 C atoms.This type of example comprises oxalic acid two hydrazides, propanedioic acid two hydrazides, amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, sebacic dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides and/or isophthalic dihydrazide.Special concern as follows: adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide.Suitable compound with oxyamine or oxime ether group for example have among the WO 93/25588 specified those.
By suitable interpolation aqueous polymer dispersions PD), also can produce surface-crosslinked in addition.This type of interpolation comprises for example adds photoinitiator or siccative.Suitable photoinitiator has those of sunlight hits, and example is the benzophenone or derivatives thereof.Suitable siccative have recommend to be used for aqueous alkide resin, based on the metallic compound (at U.Poth, Polyester und Alkydharze summarizes among 2005, the 183 pages of f. of Vincentz Network) of for example Co or Mn.
Described linked is based on being used for the monomeric gross weight of polymeric (comprising described linking agent) meter preferably with 0.0005 weight % to 5 weight %, more preferably 0.001 weight % to 2.5 weight %, the more especially amount use of 0.01 weight % to 1.5 weight %.In a concrete deformation program, described letex polymerization is used based on gross weight meter 98 weight % that can polymeric compounds, more preferably at least 99 weight %, more especially at least 99.5 weight %, especially single ethylenically unsaturated compounds of 100 weight % at least.
A specific embodiments is not for comprising the polymeric dispersions (PD) of crosslinking copolymerization agent.
Described monomer mixture M) radical polymerization can be carried out in the presence of at least a conditioning agent.Conditioning agent is based on being used for the monomeric gross weight meter of polymeric preferably with 0.0005 weight % to 5 weight %, more preferably 0.001 weight % to 2.5 weight %, the more especially amount use of 0.01 weight % to 1.5 weight %.
Conditioning agent (polymerization regulator) is the common name with compound of higher transfer constant.
Conditioning agent accelerating chain shift reaction causes that the polymerization degree of the polymkeric substance that forms reduces, and does not influence overall reaction rate.Conditioning agent can be divided into simple function, two senses or multifunctional conditioning agent, and this depends on the quantity of functional group in the molecule that can cause one or more chain transfer reactions.Suitable conditioning agent for example is recorded in J.Brandrup by K.C.Berger and G.Brandrup comprehensively, E.H.Immergut, Polymer Handbook, the 3rd edition, John Wiley ﹠amp; Sons, NewYork, 1989, in the II/81-II/141 page or leaf.
The example of suitable adjustable agent comprises aldehyde such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde-n and isobutyric aldehyde.
Also spendable other conditioning agents are as follows: formic acid, its salt or ester such as ammonium formiate, 2,5-phenylbenzene-1-hexene, sulfovinic acid ammonium and hydroxyl ammonium phosphate.
Suitable in addition conditioning agent has halogen compounds, and example is an alkyl halide, as tetracol phenixin, chloroform, bromo-trichloromethane, bromofom, allyl bromide 98 and benzylated title compound such as phenmethyl chlorine or phenmethyl bromine.
Suitable in addition conditioning agent has allylic cpd, and as allyl alcohol, functionalized allyl ethers is as allyl group ethoxylate, alkyl allyl ethers or allylin.
As conditioning agent, the preferred compound that comprises constraint form sulphur that uses.
This type of examples for compounds has inorganic bisulfites, pyrosulfite and hyposulfite, or organic sulfide, disulphide, polysulfide, sulfoxide and sulfone.It comprises di-n-butyl sulphur, di-n-octyl sulphur, phenylbenzene sulphur, thiodiglycol, ethylthioethanol, diisopropyl disulfide thing, di-n-butyl disulphide, di-n-hexyl disulphide, diacetyl disulphide, di-alcohol sulfide, di-t-butyl trisulphide, methyl-sulphoxide, dialkyl sulfide, dialkyl disulphides and/or diaryl sulfide.
Suitable polymerization regulator also comprises mercaptan (contain the compound of sulphur with SH group form, be also referred to as mercaptan (mercaptan)).Preferred conditioning agent has simple function, two senses and multi-functional thiol, mercaptoalcohol and/or mercaptan carboxylic acid.Described examples for compounds has thioglycol allyl propionate, thioglycol acetoacetic ester, halfcystine, 2 mercapto ethanol, 1,3-mercaprol, 3-sulfydryl the third-1,2-glycol, 1,4-Mercaptobutanol, Thiovanic acid, 3-thiohydracrylic acid, mercaptosuccinic acid, thioglycerin, thioacetic acid, thiocarbamide, and alkyl sulfhydryl such as normal-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan.
The example that comprises two sense conditioning agents of two constraint form sulphur atoms has two sense mercaptan, for example dimercaptopropane sulphonate (sodium salt), dimercaptosuccinic acid(DMSA), dimercapto-1-propyl alcohol, dimercaptoethane, dimercaptopropane, dimercapto butane, dimercapto pentane, dimercapto hexane, ethylene glycol bisthioglycolate mercaptoethanol acid esters and butyleneglycol 3-mercaptoethanol acid esters.The example of multifunctional conditioning agent has the compound that comprises constraint form sulphur more than two.The example has trifunctional and four sense mercaptan.
The use that can separately or be bonded to each other of all described conditioning agents.A specific embodiments relates to the polymeric dispersions PD for preparing by the free-radical emulsion polymerization that adds conditioning agent.
For preparing described polymkeric substance, can be by the described monomer of initiator polymerization that forms free radical.
Initiator as radical polymerization, can use routine to be used for the peralcohol and/or the azo-compound of this purpose, example is basic metal or ammonium peroxydisulfate, the diacetyl superoxide, the dibenzoyl superoxide, the succinyl-superoxide, ditertiary butyl peroxide, t-butylperoxyl benzoate, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, peroxide-2 ethyl hexanoic acid the tert-butyl ester, tert butyl permaleic acid, cumene hydroperoxide, diisopropyl peroxydicarbamate, two (toluoyl) superoxide, two caprinoyl superoxide, two decoyl superoxide, two lauroyl peroxides, t-butylperoxy isobutylate, t-butyl peroxy-acetate, two t-amyl peroxy things, tert-butyl hydroperoxide, Diisopropyl azodicarboxylate, 2,2 ,-azo two (2-amidine propane) dihydrochloride or 2-2 '-azo-two-(2-methylbutyronitrile).The mixture of described initiator also is suitable.
Spendable initiator has reducing/oxidizing (being redox) initiator system.Described redox initiator system is generally inorganic reductive agent and a kind of organic or inorganic oxygenant and is constituted by at least a.Described oxidation component comprises and has for example above described the initiator that is used for described letex polymerization in detail.About reduction components, described compound comprises, and an alkali metal salt of sulfurous acid for example is as S-WAT, sodium bisulfite; An alkali metal salt of pyrosulphite is as Sodium Pyrosulfite; The bisulfite adduct of aliphatic aldehyde and ketone is as the acetone hydrosulphite; Or reductive agent such as hydroxyl methyl-sulfinic acid and salt or xitix.Described redox initiator system can be used with the soluble metal compound that the multivalence attitude exists with its metal component.Typical redox initiator system has, for example xitix/ferric sulfate (II)/sodium peroxydisulfate, tertbutyl peroxide/Sodium Pyrosulfite, tert-butyl hydroperoxide/hydroxyl methyl-sulfinic acid sodium.Various components, for example reduction components can also be a mixture, for example the mixture of the sodium salt of hydroxyl methyl-sulfinic acid and Sodium Pyrosulfite.
The amount of initiator is based on treating that the whole monomer meters of polymeric are generally 0.1 weight % to 10 weight %, preferred 0.1 weight % to 5 weight %.Also can in letex polymerization, use two or more different initiators.
Described polymeric dispersions PD) preparation is carried out in the presence of at least a surface active cpd usually.Summary to suitable protective colloid is seen Houben-Weyl, Methoden derorganischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961,411 to 420 pages.Suitable emulsifying agent also sees Houben-Weyl, Methoden der organischen Chemie, the 14/1st volume, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961,192 to 208 pages.
Suitable emulsifying agent has negatively charged ion, positively charged ion and nonionic emulsifying agent.As surfactant, preferably use its relative molecular weight to be usually less than the emulsifying agent of protective colloid.Especially, proved that the binding substances that only uses anionic emulsifier or use at least a anionic emulsifier and at least a nonionic emulsifying agent is suitable.
Spendable nonionic emulsifying agent has araliphatic or aliphatic nonionic emulsifying agent, example have ethoxylation monoalkyl phenol, dialkyl group phenol and trialkyl phenol (the EO degree: 3 to 50, alkyl: C 4-C 10), the ethoxylate of long-chain alcohol (the EO degree: 3 to 100, alkyl: C 8-C 36) and polyethylene/polypropylene oxides homopolymer and multipolymer.It can comprise the epoxy alkane unit of random distribution or block form copolymerization.Extremely suitable have a for example EO/PO segmented copolymer.Preferred ethoxylate (the alkyl: C that uses long chain alkanol 1-C 30, average degree of ethoxylation is 5 to 100), wherein especially preferably contain straight chain C 12-C 20Alkyl and average degree of ethoxylation are those of 10 to 50, and ethoxylation monoalkyl phenol.
The example of suitable anionic emulsifier has alkyl sulfuric ester (alkyl: C 8-C 22) an alkali metal salt and ammonium salt, the ethoxylation alkanol (the EO degree: 2 to 50, alkyl: C 12-C 18) and ethoxylated alkyl phenols (the EO degree: 3 to 50, alkyl: C 4-C 9) an alkali metal salt and the ammonium salt of sulfuric acid monoester, alkylsulphonic acid (alkyl: C 12-C 18) an alkali metal salt and ammonium salt, and alkyl aryl sulphonic acid (alkyl: C 9-C 18) an alkali metal salt and ammonium salt.Suitable in addition emulsifying agent sees Houben-Weyl, Methoden der organischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961,192-208 page or leaf.Also be suitable for and do having on one or two aromatic ring of anionic emulsifier and have C 4-C 24Two (phenylbenzimidazole sulfonic acid) ethers and/or its basic metal or the ammonium salt of alkyl.Described compound is a common practise, sees for example US-A-4,269,749; And commercially available getting can be with for example
Figure BPA00001183914400541
2A1 (Dow Chemical Company) the commercially available acquisition of form.
Suitable cationic emulsifier is preferably quaternary ammonium halide, for example trimethylammonium cetyl chloride ammonium, methyl trioctylphosphine ammonium chloride, phenmethyl triethyl ammonium chloride, perhaps N-C 6-C 20Alkyl pyridine, N-C 6-C 20Alkyl morpholine or N-C 6-C 20The quaternary ammonium compound of alkyl imidazole, for example chlorination N-lauryl pyridine.
The amount of emulsifying agent is based on treating that the monomeric amount meter of polymeric is generally about 0.01 weight % to 10 weight %, preferred 0.1 weight % to 5 weight %.
Described polymeric dispersions PD) can be in addition mixes with common auxiliary agent and additive.It comprises, for example pH regulator agent, and an alkali metal salt of reductive agent and SYNTHETIC OPTICAL WHITNER such as hydroxyl methyl-sulfinic acid is (for example available from BASF Aktiengesellschaft's
Figure BPA00001183914400551
C), complexing agent, reodorant, spices, taste-additive and viscosity modifier are as alcohol (for example glycerine, methyl alcohol, ethanol, the trimethyl carbinol, ethylene glycol etc.).Described auxiliary agent and additive can or finish the back in polymerization in initial charge, in a kind of charging and add in the polymeric dispersions.
Described polymerization is usually at 0 to 150 ℃, preferred 20 to 100 ℃, more preferably carries out under the temperature in 30 to 95 ℃ of scopes.Described polymerization is preferably carried out under barometric point, but polymerization also is possible at elevated temperatures, as under the autogenous pressure that is used for the polymeric component.In a suitable deformation program, described being aggregated under at least a rare gas element (for example nitrogen or the argon gas) existence carried out.
Polymerisation medium can be made of water separately, and perhaps the mixture by water and water miscible liquid (as methyl alcohol) constitutes.
Preferably only make water.Letex polymerization can batchwise operation, perhaps--comprises segmentation or gradient program--with charging method (feed process) form and carries out.The preferred feedstock method, wherein a part of polymerization batches (polymerization batch) or polymer seeds are used as the initial charge adding and are heated to polymerization temperature, the beginning polymerization, then usually with the charging--wherein one or more kinds comprise the monomer of respective pure form or emulsification form--of two or more spatial isolation will remain polymerization batches continuously, segmentation or with the synergetic mode of concentration gradient (superimposition) the supply zone of convergency, and keep polymerization.
The technician should understand the fine-particled polymer that term " seed polymer " is meant a kind of aqueous polymer dispersions form.Weight average particle size (weighted average, the d of seed polymer 50) be usually less than 200nm, in 10 to 150nm the scope of being everlasting.The monomer of described seed polymer constitutes not too important usually.Suitable not only has mainly by vinyl aromatic monomers, and the synthetic seed polymer also has mainly by C---more especially by vinylbenzene (so-called vinylbenzene seed)--- 1-C 10Alkyl acrylate and/or C 1-C 10Alkylmethacrylate (for example mixture of butyl acrylate and methyl methacrylate) synthetic seed polymer.Except accounting for the described principal monomer of described seed polymer weight at least 80%, more especially at least 90% usually, described seed polymer also can comprise the different monomers of copolymerized form, more especially have increase water miscible those; Example has the monomer with at least one acid functional group and/or has the water miscible neutral monomer of increase.Based on the monomeric total amount meter of the formation of described seed polymer, this type of monomeric part is no more than 20 weight %, 10 weight % more especially usually, and when this type of monomer exists, usually in the scope of 0.1 weight % to 10 weight %.
The mode that initiator is added aggregation container in the free radical aqueous emulsion polymerization process is that those of ordinary skill in the art is known.It can all be included in the initial charge of aggregation container, perhaps according to its wear rate segmentation in the free radical aqueous emulsion polymerization process or use continuously.In each case, this will depend on the chemical property and the polymerization temperature of initiator system in own known mode for those skilled in the art.Preferably a part is included in the initial charge, and remainingly is supplied to the zone of convergency according to its wear rate.
Formed dispersion can be accepted physics or chemical after-treatment reason in the polymerization behind converging operation.The example of this type of technology is useful on residual monomer reductive known technology, as the aftertreatment by the mixture of adding polymerization starter or two or more polymerization starters under suitable temperature; Use the aftertreatment of water vapour or ammonia steam to polymers soln; Or use the rare gas element desorption; Or with the processing of oxygenant or reductive agent to reaction mixture; Adsorption technology, as with impurity absorption at selected medium for example on the gac; Or for example ultrafiltration.
Solids content in the resulting aqueous polymer dispersions (PD) is generally 20 weight % to 70 weight % based on described polymeric dispersions meter, preferred 40 weight % to 60 weight %.Described solids content is understood to include the highly-branched polymer that is added.The second-order transition temperature T of existing emulsion polymer in the described polymeric dispersions gPreferably at-50 to 80 ℃, more preferably-10 to 50 ℃ scope.
Gained aqueous polymer dispersions PD) can with itself or with the mixture of other polymkeric substance (being generally film-forming polymer), use with the binder composition in the water-based coating material (as coating material or paint mixture).
The present invention also provides a kind of aforesaid aqueous polymer dispersions (PD) or binder composition of constituting of polymer dispersion (PD) thus of comprising.This binder composition also comprises one or more and is added into described highly-branched polymer in the described polymeric dispersions (PD).
Except described polymeric dispersions (PD), described binder composition can comprise at least a other film-forming polymer.Comprising for example Synolac.The example of suitable Synolac has water soluble alkyd resin, and its weight average molecular weight is preferably 5000 to 40000.Suitable in addition have weight average molecular weight greater than 40000, especially greater than 100000 Synolac.Synolac is the polyester (U.Poth, Polyester und Alkydharze, Vincentz Network 2005) with esterifications such as siccative oil, lipid acid.
Suitable water soluble alkyd resin has enough high acid values, the preferred Synolac in 30 to 65mg KOH/g scopes.If suitable, its can partly or entirely be in and form.Weight average molecular weight is preferably 8000 to 35000, and more preferably 10000 to 35000.
---especially improving the Synolac of VOC content in the coating material---is not preferred in some cases to use this type of other film-forming polymer.Therefore, a particular embodiment is a kind of like this coating material, and it comprises at least a dispersion PD) and at least a highly-branched polymer, but do not have the film-forming polymer beyond the existing emulsion polymer in the described polymeric dispersions.
Binder composition of the present invention preferably uses with water-based coating material form.The form of described coating material has, for example unpigmented system (transparent varnish) or coloured system.The part of described pigment can be described by pigment volume concentration (PVC) (PVC).PVC has described pigment volume (V P) and weighting agent volume (V F) with by the tackiness agent volume (V of dry coating film B), the per-cent of the cumulative volume that constitutes of pigment volume and weighting agent volume: PVC=(V P+ V F) * 100/ (V P+ V F+ V B).Coating material can be for example based on the following classification of PVC:
Highly-filled interior paint, washable, white/matt about 85
Interior paint, scrubbing resistance, white/tarnish about 80
Semi-gloss paint, mercerising-tarnish about 35
Semi-gloss paint, mercerising about 25
External application masonry paint, the about 45-55 of white
Transparent varnish 0
The present invention also provides a kind of coating material of waterborne compositions form, and it comprises:
-a kind of aforesaid binder composition that comprises highly-branched polymer as additive,
-randomly at least a inorganic filler and/or at least a mineral dye,
-randomly other auxiliary agent and
-water.
In first preferred deformation program, coating material of the present invention is applicable to the transparent varnish that does not comprise pigment pigment and weighting agent that preparation has higher freeze/thaw stability.
In second particularly preferred deformation program, coating material of the present invention is applicable to the emulsion paint that preparation has higher freeze/thaw stability.
The coating material that preferably comprises following material:
-at least a PD of polymeric dispersions as defined above of solid contents 10 weight % to 60 weight %),
Inorganic filler and/or the mineral dye of-10 weight % to 70 weight %,
The typical auxiliary agent of-0.1 weight % to 20 weight % and
-supply the water of 100 weight %.
PD as above-mentioned coating material part) based on solid, i.e. emulsion polymer and one or more highly-branched polymer, and do not have water.
The coating material of the present invention of waterborne compositions form is preferably used as coating.One embodiment of the invention relate to the coating material of transparent varnish form.Another embodiment of the invention comprises the coating material of emulsion paint form.Of the present invention have the color coating material to adopt for example water-based half light or high gloss paint form.
Set forth hereinafter the composition of typical emulsion paint.Emulsion paint comprises the non-volatility composition of 30 weight % to 75 weight %, preferred 40 weight % to 65 weight % usually.This is meant all the components in the preparation that is not water, and is the gross weight of tackiness agent, weighting agent, pigment, low voc solvent (boiling point is more than 220 ℃), softening agent and reagent and additive in polymerization for example at least.The scope that calculates this numerical value is for about
A) 3 weight % to 90 weight %, the fine-particled polymer dispersions PD of 10 weight % to 60 weight % more especially,
B) 0 weight % to 85 weight %, preferred 5 weight % to 60 weight %, at least a mineral dye of 10 weight % to 50 weight % more especially,
C) 0 weight % to 85 weight %, more especially 5 weight % to 60 weight % inorganic filler and
D) 0.1 weight % to 40 weight %, the typical auxiliary agent of 0.5 weight % to 20 weight % more especially.
In order to all pigment of comprehensive finger and weighting agent, example is coloured pigment, white pigment and inorganic filler to term " pigment " in the context of the invention.It comprises inorganic white pigment, as titanium dioxide (preferably with rutile form), barium sulfate, zinc oxide, zinc sulphide, basic lead white, ANTIMONY TRIOXIDE SB 203 99.8 PCT, lithopone (zinc sulphide+barium sulfate); Or coloured pigment, for example ferric oxide, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, prussian blue or urania green (Schweinfurt green).Except described mineral dye, emulsion paint of the present invention also can comprise organic color pigment, example is sepia, gamboge, cologne earth, toluidine red, p-nitroaniline red, organic yellow, indigo, azoic dyestuff, cyan (anthraquinonoid) and indigoide colors, and dioxazine, quinacridone, phthalocyanine pigment, isoindolinone and metal-complexing pigment.Suitable have bubble in addition increasing the synthetic white pigment of scattering of light, as Dispersion.
Suitable weighting agent has, and aluminosilicate for example is as feldspar; Silicate is as kaolin, talcum, mica, magnesite; Alkaline earth metal carbonate is as lime carbonate, magnesiumcarbonate, the rhombspar with for example calcite or chalk form; Alkaline earth metal sulphate is as calcium sulfate; Silicon-dioxide etc.Certainly the particulate weighting agent is preferred in coating material.Described weighting agent can use with separate constituent.But in actual practice, proved that filler mixture is specially suitable, example has lime carbonate/kaolin and lime carbonate/talcum.There is the coating material of light to generally include only a spot of superfine particle weighting agent.
The particulate weighting agent also can be in order to the use that improves opacifying power and/or save white pigment.For regulating opacifying power, color harmony depth of shade, preferably use the mixture of coloured pigment and weighting agent.
Can---to be the volume of pigment and the ratio of the cumulative volume of dry paint---by pigment volume concentration (PVC) (PVC) describe the part of pigment.For example the PVC of gloss paint is 12% to 35%, in preferred 15% to 30% the scope.
Except described polymeric dispersions PD), coating material of the present invention (water-based coating material) is if can comprise at least a highly-branched polymer as additive--and suitable other film-forming polymer and pigment, other auxiliary agent.
Except the emulsifying agent that uses in the polymerization, typical auxiliary agent comprises wetting agent or dispersion agent, as sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, the an alkali metal salt of acrylic copolymer or copolymer-maleic anhydride and ammonium salt, polyphosphate such as 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sodium, the salt of naphthene sulfonic acid, more especially its sodium salt.
Proper auxiliary agent has flow control agent, defoamer, biocide and thickening material in addition.Suitable thickening has, for example associative thickeners such as polyurethane thickener.The amount of described thickening material preferably is lower than 1 weight % based on the solid content meter of described coating material, more preferably less than 0.6 weight %.
Coating of the present invention is preparation in a known way in the following manner: the mixing device that is used for this purpose in routine mixes described component.Find suitable to be: if by pigment, water--and suitable auxiliary agents--preparation water-based lotion or dispersion, mixed polymerization tackiness agent then--promptly generally speaking, the aqueous dispersion of polymkeric substance--with pigment lotion or pigment dispersion.
Coating of the present invention comprises 30 weight % to 75 weight %, the non-volatility composition of preferred 40 weight % to 65 weight % usually.This is meant all the components in the preparation of non-water, but is the total amount in tackiness agent, pigment and the auxiliary agent of the solid contents of described coating at least.Described volatile component mainly is a water.
Suitable coating is high gloss paint.The glossiness of coating can be determined according to DIN 67530.Described coating is applied to sheet glass and at room temperature dry 72 hours with the slot width of 240 μ m.Test sample is inserted calibrated reflexometer, and with the input angle of determining, the light of measuring reflection or scattering returns degree.Reflectometer value is as measuring of glossiness definite (value is high more, and glossiness is high more).
The glossiness of high gloss paint preferably in the time of 20 ° greater than 60, in the time of 60 ° greater than 80.Reflectometer value is determined at 23 ℃, and with the non-dimensional parameter record as the input angle function, is 40 in the time of 20 ° for example.
Coating of the present invention can---for example by being coated with shop, spraying, dip-coating, roller coating, blade coating etc.---be applied to matrix in a usual manner.
It is preferably used as building coating, promptly is coated on building or part building.Described matrix can be mineral substrate, as the ash end, gypsum or plasterboard, masonry or concrete, timber, wood materials, metal or paper wallpaper or plastics PVC for example for example.
Described coating is preferred for building interior, as interior wall, inside door, panelling, handrail, furniture etc.
Coating characteristic of the present invention be easy to handle, good working properties and high covering power.Its pollutant load is lower.It has good usefulness character, as high water-repellancy, good wet tack (particularly alkydpaints), high conglutination-resistance, good recoatability and the good flowability of using.The equipment that uses is easy to water and cleans.
Illustrate the present invention in more detail with reference to following non-limiting examples.
Embodiment:
I. highly-branched polymer is synthetic
HBP 1: hyperbranched polycarbonates
In the 6l flask of agitator, internal thermometer and reflux condensing tube is housed, make 1183.0g diethyl carbonate (10.00mol) and 2700.0g by the trivalent alcohol (10.00mol) that obtains in advance with three ethylene oxide unit ethoxylated trimethylolpropane under the situation that salt of wormwood (0.5g) exists, at barometric point and gentleness is blown into nitrogen and in about 130 ℃ of reactions down.The ethanol that forms in reaction process made the boiling point of reaction mixture reduce to 100 ℃ in 4 hours.Keep when constant when boiling temperature, use the water distilling apparatus that constitutes by the packed column of 20cm, descending prolong and collector to replace reflux condensing tube, and the ethanol of formation in will reacting not engler distillation remove.When removing the about 810g ethanol of total amount when (be equivalent to the alcoholic acid total conversion rate and be about 88%), reaction mixture is cooled to 100 ℃, and by to add concentration be in 85% the phosphoric acid (0.5g) and salt of wormwood until pH less than 7.Under 100 ℃, this mixture was stirred 1 hour again.Then, in 10 minutes, remove remaining monomer and remaining ethanol under 140 ℃ and 40 millibars.Cooling afterwards is assay products also.
The OH number is 265mg KOH/g; (elutriant=DMAC, calibration=PMMA) definite molecular weight is M by GPC n=2100g/mol and M w=7400g/mol.
HBP 2: hyperbranched polycarbonates
In 61 flasks of agitator, internal thermometer and reflux condensing tube are housed, make 590.7g diethyl carbonate (5.00mol) and 3350.0g by the trivalent alcohol (5.00mol) that obtains in advance with 12 ethylene oxide unit ethoxylated trimethylolpropane under the situation that salt of wormwood (0.5g) exists, at barometric point and gentleness is blown into nitrogen and in about 140 ℃ of reactions down.The ethanol that forms in reaction process made the boiling point of reaction mixture reduce to 120 ℃ in 4 hours.Keep when constant when boiling temperature, use the water distilling apparatus that constitutes by the packed column of 20cm, descending prolong and collector to replace reflux condensing tube, and the ethanol of formation in will reacting not engler distillation remove.When removing the about 405g ethanol of total amount when (be equivalent to the alcoholic acid total conversion rate and be about 88%), reaction mixture is cooled to 100 ℃, by to add concentration be in 85% the phosphoric acid (0.5g) and salt of wormwood until pH less than 7.Under 100 ℃, this mixture was stirred 1 hour again.Then, in 10 minutes, remove remaining monomer and remaining ethanol under 140 ℃ and 40 millibars.Cooling afterwards is assay products also.
The OH number is 146mg KOH/g; (elutriant=DMAC, calibration=PMMA) definite molecular weight is M by GPC n=2700g/mol and M w=5500g/mol.Find that by DSC second-order transition temperature is Tg=-56 ℃.
II. the preparation of polymeric dispersions
Dispersion D1:
The dispersion of vinylformic acid, acrylamide, n-butyl acrylate and methyl methacrylate
Initial charge: 32.80g charging 1
10.92g charging 2
201.24g complete softening water
0.13g copper sulfate (II) (0.1%)
3.25g Maranil A
Figure BPA00001183914400621
(20%) (just-(C 10-C 13Alkyl)
Benzene sulfonic acid sodium salt, Cognis)
The complete softening water of additive 1:7.22g
The complete softening water of charging 1:248.09g
8.67g Dowfax
Figure BPA00001183914400622
(45%) (alkyl diphenyl ether disulphonic acid
Salt, Dow)
26.00g Lutensol TO
Figure BPA00001183914400623
(20%) (ethoxylation C 13
Oxo alcohol, BASF Aktiengesellschaft)
8.45g vinylformic acid
19.50g acrylamide (concentration is 50% in water)
364.00g n-butyl acrylate
267.80g methyl methacrylate
Charging 2:31.20g sodium peroxydisulfate (2.5%)
The complete softening water of charging 3:3.90g
2.6g ammoniacal liquor (25%)
The complete softening water of charging 4:5.92g
3.90g tert-butyl hydroperoxide (10%)
The complete softening water of charging 5:9.3g
4.96g acetone hydrosulphite (13.10%)
The complete softening water of charging 6:37.90g
Charging 7:4.35g Acticid MBS (5%) (biocide,
Thor-Chemie)
Charging 8:11.05g aqueous sodium hydroxide solution (10%)
11.57g complete softening water
At first with the complete softening water, copper sulfate (II) of the described amount that belongs to initial charge and
Figure BPA00001183914400631
A20 gives the aggregation container charging that measuring apparatus and thermoswitch are housed, and under agitation this initial charge is heated to 95 ℃.Next the charging 1 that adds initial amount of filler, and with this mixture stirring 10 minutes.Add the charging 2 of initial charge amount afterwards, and this initial charge was carried out partially polymerized 5 minutes.After partially polymerized, in 150 minutes, be metered into remaining charging 1 and 2, after charging 1 finishes, it washed with additive 1.Polymerization was continued 15 minutes, during this period with the temperature regulation to 90 of reaction vessel ℃.Be metered into charging 3 then with neutralization in 15 minutes, then parallel charging 4 and 5 of being metered in 1 hour continue to stir more than 15 minutes afterwards.Next in 90 minutes, will react batch of material and be cooled to 30 ℃, after it reaches this temperature, add charging 6.At last, under 30 ℃, add charging 7 and 8 equally in succession, will react batch of material thereafter and be cooled to room temperature.
Table 1: analyze
D1
pH 8.1
Coagulum (g) 1
Granular size (nm) 141
MFFT(℃) 0
Solids content (%) 50
LT(％) 89
Tg(℃) 8
Viscosity (Z2) 100l/s 391
III. performance embodiment
1. the preparation of water-borne coatings
Under the stirring of using band tooth disk stirrer, various components are metered into specified amount (weight part) in the table 2 and order.Before adding dispersion D1, at first, under 1000rpm, add remaining ingredient equally thereafter by under 1000rpm, disperseing to prepare a kind of lotion in 15 minutes.It is smooth until the pigment lotion to continue dispersion, does not promptly lump.Prior hybrid dispersions D1 and hyperbranched polymer.Comparative formulations F1 does not comprise hyperbranched polymer.
Table 2: coating formulation
Figure BPA00001183914400641
Table 3: result
F1 relatively F2 F3 F4 F5 F6
Initial viscosity (Brookfield) mPa.s 3380 3220 3120 3040 2860 3080
Freeze/thaw stability (℃) -18 -18 -18 -18 -18 -8
Viscosity circulation 1 5580 4600 4180 3800 3420 4560
Viscosity circulation 2 6280 4740 4420 4020 3560 5300
Viscosity circulation 3 6460 4600 4500 4080 3600 5320
Viscosity circulation 4 6280 4560 4500 4100 3660 5320
Viscosity circulation 5 6340 4620 4480 4060 3500 5320
Microgel particle grade (wetting) 4 3 2 3 3 4
Microgel particle grade (doing) 2 1-2 0-1 1 1-2 1-2
The denseness of coating after the testing campaign Creaminess Creaminess-fluid Creaminess-fluid Fluid Fluid Creaminess-fluid
Brookfield (Brookfield) viscosity is determined with axle 6 down at 23 ℃;
Scrape paint film with 60 μ m scrapers;
Microgel particle grade (gel speck rating): 0 (=fabulous) to 6 (=extreme differences)

Claims (20)

1. one kind prepares a kind of aqueous polymer dispersions PD with improved freeze/thaw stability) method, described method is by making at least a ethylenically unsaturated monomers M) free-radical emulsion polymerization and add at least a highly-branched polymer and realize.
2. the process of claim 1 wherein that the highly-branched polymer of using is at least a hyperbranched polymer as additive.
3. the method for claim 2, the degree of branching DB of wherein said hyperbranched polymer is 10% to 95%, and is preferred 25% to 90%, more especially 30% to 80%.
4. each method during aforesaid right requires, wherein said highly-branched polymer is selected from polycarbonate, polyester, polyethers, urethane, polyureas, polyamine, polymeric amide, poly-(Semicarbazido manthanoate), poly-(ether amine), poly-(ester amine), poly-(ether acid amides), poly-(esteramides), poly-(amido amine), poly-(ester carbonic ether), poly-(ether carbonate), poly-(ether-ether), poly-(ether-ether carbonic ether) and composition thereof.
5. each method in the claim 1 to 4, wherein said highly-branched polymer is hyperbranched polycarbonates, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether), perhaps comprises the mixture of the hyperbranched polymer of at least a hyperbranched polycarbonates, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether).
6. each method during aforesaid right requires, wherein said monomer M) be selected from α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 1-C 20The ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30Monocarboxylic ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide, single ethylenic unsaturated carboxylic acid and sulfonic acid, phosphorus monomer, α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 2-C 30The ester of alkane glycol, α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and comprise primary amino or the C of secondary amino group 2-C 30The acid amides of amino alcohol, α, β-ethylenic unsaturated monocarboxylic acid and N-alkyl and N, the primary amide of N-dialkyl derivatives, N-vinyl lactam, open chain N-vinylamide compound, allyl alcohol and C 1-C 30Monocarboxylic ester, α, ester, the α of β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and amino alcohol, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and comprise acid amides, the N of the diamines of at least one primary amino or secondary amino group, N-diallyl amine, N, N-diallyl-N-alkylamine, the nitrogen heterocyclic, vinyl ether, the C that are replaced by vinyl and allyl group 2-C 8Monoolefine, the non-aromatic hydrocarbon that contains at least two conjugated double bonds, polyethers (methyl) acrylate, comprise monomer of urea groups and composition thereof.
7. each method during aforesaid right requires, wherein at least 40 weight %, preferred at least 60 weight %, at least a following monomer M 1 that is selected from of at least 80 weight % are more especially used in letex polymerization) carry out: α, β-ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and C 1-C 20The ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30Monocarboxylic ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide and composition thereof.
8. the method for claim 7, wherein letex polymerization use in addition up to 60 weight %, preferably up to 40 weight %, more preferably up at least a following monomer M 2 that is selected from of 20 weight %) carry out: the acid anhydrides of ethylenic unsaturated monocarboxylic acid and di-carboxylic acid and ethylenic unsaturated dicarboxylic acid and monoesters, (methyl) acrylamide, C 1-C 10Hydroxyalkyl (methyl) acrylate, C 1-C 10Hydroxyalkyl (methyl) acrylamide and composition thereof.
9. each method was wherein added described highly-branched polymer and is carried out after letex polymerization during aforesaid right required.
10. pass through the aqueous polymer dispersions PD of the method acquisition of each definition in the claim 1 to 9).
11. comprise the aqueous polymer dispersions PD that the method by each definition in the claim 1 to 9 obtains), the binder composition of at least a highly-branched polymer and randomly at least a other film-forming polymer.
12. the coating material of a waterborne compositions form, it comprises
-as in the claim 11 definition binder composition,
-randomly at least a inorganic filler and/or at least a mineral dye,
-randomly other auxiliary agent and
-water.
13. the coating material of the claim 12 of coating form.
14. the coating of the claim 13 of transparent varnish form.
15. the coating of the claim 13 of emulsion paint form.
16. the method for a freeze/thaw stability improvement aqueous polymer dispersions PD), wherein said aqueous polymer dispersions PD) be by at least a ethylenically unsaturated monomers M) free-radical emulsion polymerization obtain, described method realizes by adding at least a highly-branched polymer.
17. the highly-branched polymer of each definition is used to improve the purposes of freeze/thaw stability at least a claim 1 to 5 as the additive of aqueous polymer dispersions.
18. at least a highly-branched polymer is used to improve the purposes of the freeze/thaw stability of described product as the product additive that comprises emulsion polymer, described emulsion polymer is based on the ethylenically unsaturated monomers M of each definition at least a claim 6 to 8).
19. the purposes of claim 18 as paint additive, more especially is used as the additive of transparent varnish or emulsion paint.
20. comprise in the claim 1 to 5 defined highly-branched polymer in each as the aqueous polymer dispersions PD of additive) as the purposes of coating composition.
CN200880125005XA 2007-11-19 2008-11-19 Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability Expired - Fee Related CN101910207B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP07121032.2 2007-11-19
EP07121032 2007-11-19
EP07150042 2007-12-14
EP07150042.5 2007-12-14
PCT/EP2008/065860 WO2009065867A1 (en) 2007-11-19 2008-11-19 Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability

Publications (2)

Publication Number Publication Date
CN101910207A true CN101910207A (en) 2010-12-08
CN101910207B CN101910207B (en) 2013-04-24

Family

ID=40292430

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200880125005XA Expired - Fee Related CN101910207B (en) 2007-11-19 2008-11-19 Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability

Country Status (8)

Country Link
US (1) US8309646B2 (en)
EP (1) EP2222716A1 (en)
JP (1) JP2011503336A (en)
KR (1) KR20100100891A (en)
CN (1) CN101910207B (en)
AU (1) AU2008327942A1 (en)
BR (1) BRPI0820427A2 (en)
WO (1) WO2009065867A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103608399A (en) * 2011-04-06 2014-02-26 斯蒂潘公司 Multi-arm hydrophilic urethane polymers, methods of making them, and compositions and processes employing them
CN104640909A (en) * 2012-09-20 2015-05-20 巴斯夫欧洲公司 Hyperbranched phosphoric acid esters
CN107523155A (en) * 2016-06-21 2017-12-29 立邦涂料（中国）有限公司 A kind of water-soluble polymer antifreeze
CN109925589A (en) * 2019-03-05 2019-06-25 江苏长寿棒科技有限公司 A kind of novel prostate dilator
CN111962284A (en) * 2020-08-15 2020-11-20 绍兴兴隆染织有限公司 Printing and dyeing process of polyester fabric
CN114929817A (en) * 2019-12-30 2022-08-19 巴斯夫涂料有限公司 Coating materials containing branched polyester polyols as plasticizers

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009147126A1 (en) * 2008-06-03 2009-12-10 Basf Se Titanium dioxide composition comprising titanium dioxide nanoparticles, and preparation and use thereof
US8722796B2 (en) * 2010-01-20 2014-05-13 Basf Se Process for preparing an aqueous polymer dispersion
US8530567B2 (en) * 2010-02-18 2013-09-10 Basf Se Polymer dispersion which comprises a highly branched polycarbonate having unsaturated fatty acid groups
ES2583302T3 (en) 2010-02-18 2016-09-20 Basf Se Polymeric dispersion containing a highly branched polycarbonate with unsaturated fatty acid groups
US20140235776A1 (en) * 2011-07-28 2014-08-21 Angus Chemical Company Aminoalcohol compounds and their use as zero or low voc additives for paints and coatings
WO2013119521A1 (en) 2012-02-10 2013-08-15 Arkema Inc. Latex binders useful in zero or low voc coating compositions
CA2960100A1 (en) 2016-03-28 2017-09-28 Dow Global Technologies Llc Aqueous compositions having polyalkoxylate salts for improved open time
CA2960249A1 (en) 2016-03-28 2017-09-28 Dow Global Technologies Llc Aqueous compositions having polyalkoxylates for improved open time
WO2017222473A1 (en) * 2016-06-21 2017-12-28 Nipsea Technologies Pte Ltd Anti-freeze agents
KR102644544B1 (en) 2016-09-21 2024-03-11 넥스트큐어 인코포레이티드 Antibodies for SIGLEC-15 and methods of using the same
US10053533B1 (en) 2017-04-13 2018-08-21 Presidium Usa, Inc. Oligomeric polyol compositions
KR102285155B1 (en) * 2021-01-15 2021-08-02 이규선 Paint composition and hybrid nano coating film formed therefrom
DE112022004690T5 (en) 2021-09-28 2024-07-18 Kemet Electronics Corporation ADVANCED POLYMER DISPERSION AND A CAPACITOR BASED ON IT

Family Cites Families (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1329126A (en) 1969-12-11 1973-09-05 Mitsubishi Rayon Co Acrylic fibre and a method for manufacturing the same
JPS5033767B1 (en) 1971-03-11 1975-11-04
DE2722097C3 (en) 1977-05-16 1981-09-17 Basf Ag, 6700 Ludwigshafen (Meth) acryloxy-alkylpropanals, process for their preparation and use thereof
US4226007A (en) 1979-03-16 1980-10-07 Signode Corporation Sealless strap connection
US4269749A (en) 1979-04-30 1981-05-26 The Dow Chemical Company Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions
DE3721766A1 (en) * 1987-07-01 1989-01-12 Bayer Ag MIXTURES OF ELASTOMER-LATICES AND DISPERSIONS OF AROMATIC POLYCARBONATES, POLYESTERS OR POLYESTER CARBONATES AND PRODUCTS MADE THEREOF
DE4219384A1 (en) 1992-06-13 1993-12-23 Basf Ag Dispersion or solution which can be crosslinked at room temperature with hydroxylamines or oxime ethers
DE19524045A1 (en) 1995-07-01 1997-01-02 Basf Ag Highly functionalized polyurethanes
US5786429A (en) 1996-04-18 1998-07-28 Hercules Incorporated Highly branched polyamidoamines and their preparation
NL1007186C2 (en) 1997-10-01 1999-04-07 Dsm Nv ß-hydroxyalkylamide group-containing condensation polymer.
US6150468A (en) * 1998-11-12 2000-11-21 National Starch And Chemical Investment Holding Corporation Water soluble amphiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization
GB9824932D0 (en) 1998-11-16 1999-01-06 Ici Ltd Coating composition
DE19947631A1 (en) 1998-12-22 2000-06-29 Bayer Ag Process for the preparation of highly branched polyols based on glycidol
DE19904444A1 (en) 1999-02-04 2000-08-10 Basf Ag Dendrimers and highly branched polyurethanes
SE514207C2 (en) 1999-03-23 2001-01-22 Perstorp Ab Hyperbranched dendritic polyether and process for its preparation
US6534590B1 (en) * 1999-10-29 2003-03-18 Dow Corning Toray Silicone Co., Ltd. Silicone-grafted vinyl copolymer emulsion composition
US6569956B1 (en) 1999-12-22 2003-05-27 Basf Corporation Hyperbranched polyol macromolecule, method of making same, and coating composition including same
DE10013187A1 (en) 2000-03-17 2001-10-11 Basf Ag Highly functional polyisocyanates
AU2000251762A1 (en) 2000-06-02 2001-12-24 National Starch And Chemical Investment Holding Corporation Water soluble ampiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization
DE10030869A1 (en) 2000-06-23 2002-01-03 Basf Ag Multifunctional polyisocyanate polyaddition products
US6692840B1 (en) 2000-09-15 2004-02-17 National Starch And Chemical Investment Holding Corporation Polymer coating for rubber articles
US6420479B1 (en) * 2000-12-29 2002-07-16 National Starch And Chemical Investment Holding Corporation Star polymer colloidal stabilizers
US6534600B2 (en) 2001-03-26 2003-03-18 Michigan Molecular Institute Hyperbranched polyureas, polyurethanes, polyamidoamines, polyamides and polyesters
DE10138216A1 (en) 2001-08-03 2003-02-20 Bayer Ag Production of aliphatic polycarbonate polymer e.g. poly(ether-carbonate) polyol, involves ring-opening polymerization of cyclic carbonate in the presence of double metal cyanide catalyst
DE10147712A1 (en) 2001-09-27 2003-04-17 Basf Ag Process for the production of aliphatic polycarbonates
DE10163163A1 (en) 2001-12-20 2003-07-03 Basf Ag Process for the production of highly functional, hyperbranched polyester by enzymatic esterification
SE524461C2 (en) 2002-01-25 2004-08-10 Perstorp Specialty Chem Ab Chain extended dendritic polyether, composition and use thereof
DE10204979A1 (en) 2002-02-06 2003-08-14 Basf Ag Process for the production of highly functional highly branched polyureas
DE10211664A1 (en) 2002-03-15 2003-10-02 Hyperpolymers Gmbh Preparation of highly branched polyols based on glycosides useful as an additive in paints and adhesives, additive and crosslinker in polymers, in cosmetics, preparation of nano particles and active substance carrier
DE10219508A1 (en) 2002-04-30 2003-11-13 Basf Ag Process for the production of highly functional, hyperbranched polyester
SE524961C2 (en) 2002-08-16 2004-11-02 Celanese Emulsions Norden Ab Waterborne copolymer dispersion and its use in coatings
DE10240817A1 (en) 2002-08-30 2004-03-11 Basf Ag Process for the production of hyperbranched, water-soluble polyester
SE524960C2 (en) 2003-02-12 2004-11-02 Celanese Emulsions Norden Ab Polymerization process at elevated pressure in the presence of dendritic polymer
SE526998C2 (en) 2003-07-01 2005-12-06 Celanese Emulsions Norden Ab Process for preparing an aqueous copolymer dispersion, and use thereof
DE10331770A1 (en) 2003-07-11 2005-02-03 Basf Ag Process for the preparation of hyperbranched polymers
EP1664154B1 (en) 2003-09-12 2009-05-27 Basf Se Highly functional, highly branched or hyperbranched polycarbonates and the production and use hereof
DE10351401A1 (en) 2003-11-04 2005-06-09 Basf Ag Highly functional, highly branched polyureas
US7612126B2 (en) 2003-12-04 2009-11-03 Basf Aktiengesellschaft Low-VOC aqueous coating compositions with excellent freeze-thaw stability
DE102004006304A1 (en) 2004-02-09 2005-08-25 Basf Ag Highly functional, highly branched polyureas
DE102004039101A1 (en) 2004-08-11 2006-02-23 Basf Ag Process for the preparation of hyperbranched polyamides
EP1879551A2 (en) 2005-02-21 2008-01-23 Basf Aktiengesellschaft Active substance composition comprising at least one nitrogen atom-containing, hyperbranched polymer
DE102005009166A1 (en) 2005-02-25 2006-08-31 Basf Ag Use of high-functional, hyper branched polycarbonate (obtained by preparing condensation products either by reacting organic carbonates with an aliphatic, aliphatic/aromatic or aromatic alcohol), as solvent auxilary agent
DE102005056592A1 (en) 2005-11-25 2007-05-31 Basf Ag Novel uncrosslinked, hyperbranched polylysines useful as e.g. adhesive aids, thixotropic agents or phase transfer agents are obtained by catalytic reaction of a salt of lysine with an acid and optionally with comonomers
DE102005060783A1 (en) 2005-12-16 2007-06-28 Basf Ag Highly functional, hyperbranched polymers and a process for their preparation
CN101405661A (en) 2006-03-22 2009-04-08 巴斯夫欧洲公司 Substrates coated with branched polyurethanes for electrophotographic printing processes
US7753998B2 (en) 2006-03-29 2010-07-13 Turtle Wax, Inc. Liquid polishing composition and kit
EP2015730A1 (en) 2006-04-28 2009-01-21 Basf Se Method for solubilising hydrophobic active substances in an aqueous medium
EP2029657A2 (en) 2006-05-19 2009-03-04 BASF Coatings AG Powder coating materials with high-functionality, highly branched or hyperbranched polycarbonates
KR20090019858A (en) 2006-05-23 2009-02-25 바스프 에스이 Use of hyperbranched polycarbonates as a dispersing agent for pigments
MX2008015022A (en) 2006-06-08 2008-12-05 Basf Se Composite materials on the basis of polyurethanes with improved adhesion.
JP2009543909A (en) 2006-07-20 2009-12-10 ビーエーエスエフ ソシエタス・ヨーロピア Water-based paint containing highly functional, highly branched or hyperbranched polycarbonate
MX2009000067A (en) 2006-07-26 2009-01-23 Basf Se Highly functional, hyperbranched polycarbonates and production and use thereof.
US20080098927A1 (en) * 2006-10-26 2008-05-01 Xerox Corporation Pigmented phase change inks
JP2010509478A (en) 2006-11-14 2010-03-25 ビーエーエスエフ ソシエタス・ヨーロピア Hyperbranched or hyperbranched polyesters and their production and use
JP2010509480A (en) 2006-11-15 2010-03-25 ビーエーエスエフ ソシエタス・ヨーロピア Improved adhesive layer material comprising elastic polyurethane binder and plastic granules
JP2010512439A (en) 2006-12-11 2010-04-22 ビーエーエスエフ ソシエタス・ヨーロピア High elastic polyurethane foam
JP2010513581A (en) 2006-12-15 2010-04-30 ビーエーエスエフ ソシエタス・ヨーロピア Production of polymer dispersions in the presence of organic polymer particles.
BRPI0721119A2 (en) 2006-12-15 2015-01-27 Basf Se WATER POLYMERIC DISPERSION, PROCESS FOR THE PREPARATION OF THEREOF, METHOD OF MODIFICATION OF THE RHEOLOGICAL PROPERTIES OF A WATER POLYMERIC DISPOSAL, AGRICULTURAL COATING MATERIAL, USES OF A POLYMERICAN ALTERNATE POLYMERICANT DISPOSAL FOLDER FOR PAPER COATING, AND, PAPER OR PAPER
WO2008074687A2 (en) 2006-12-19 2008-06-26 Basf Se Thermoplastic moulding compositions having improved ductility
ES2510548T3 (en) 2007-03-22 2014-10-21 Basf Se Hyperbranched Polyesters

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103608399A (en) * 2011-04-06 2014-02-26 斯蒂潘公司 Multi-arm hydrophilic urethane polymers, methods of making them, and compositions and processes employing them
CN103608399B (en) * 2011-04-06 2015-11-25 斯蒂潘公司 The hydrophilic urethane polymers of multi-arm, prepare they method and use their composition and method
CN104640909A (en) * 2012-09-20 2015-05-20 巴斯夫欧洲公司 Hyperbranched phosphoric acid esters
US10023690B2 (en) 2012-09-20 2018-07-17 Basf Se Hyperbranched phosphoric acid esters
CN104640909B (en) * 2012-09-20 2018-11-13 巴斯夫欧洲公司 Hyperbranched phosphate
CN107523155A (en) * 2016-06-21 2017-12-29 立邦涂料（中国）有限公司 A kind of water-soluble polymer antifreeze
CN109925589A (en) * 2019-03-05 2019-06-25 江苏长寿棒科技有限公司 A kind of novel prostate dilator
CN114929817A (en) * 2019-12-30 2022-08-19 巴斯夫涂料有限公司 Coating materials containing branched polyester polyols as plasticizers
CN114929817B (en) * 2019-12-30 2024-01-05 巴斯夫涂料有限公司 Coating containing branched polyester polyol as plasticizer
CN111962284A (en) * 2020-08-15 2020-11-20 绍兴兴隆染织有限公司 Printing and dyeing process of polyester fabric

Also Published As

Publication number Publication date
KR20100100891A (en) 2010-09-15
CN101910207B (en) 2013-04-24
US20100280165A1 (en) 2010-11-04
AU2008327942A1 (en) 2009-05-28
WO2009065867A1 (en) 2009-05-28
US8309646B2 (en) 2012-11-13
JP2011503336A (en) 2011-01-27
BRPI0820427A2 (en) 2015-05-26
EP2222716A1 (en) 2010-09-01

Similar Documents

Publication Publication Date Title
CN101910207B (en) Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability
CN101868509B (en) Use of highly branched polymers in polymer dispersions for gloss colours
CN103403049B (en) The method preparing polyurethane-polyacrylate composite dispersion
CN106939060B (en) Polymer, method and composition
US7230051B2 (en) Use of polyacrylate-modified polysiloxanes as levelling agents in coating compositions
CN101605852B (en) Polymer dispersions containing highly branched polycarbonates
RU2677334C1 (en) Aqueous coating composition and production of multilayer paint systems using said coating composition
AU2015231936B2 (en) Controlled crosslinking of latex polymers with polyfunctional amines
US9976052B2 (en) Aqueous coating composition and production of multicoat paint systems using said coating composition
CN102585241A (en) High-functionality highly branched or hyperbranched polycarbonates and their preparation and use
US9404009B2 (en) Polymer dispersants
CN105848790B (en) Method for producing multicoat paint systems
CN102131764A (en) Functionalized (meth)acrylate monomer, polymer, coating agent, and production and cross-linking method
CN101652397A (en) waterborne polymeric dispersions
CN103965454A (en) Reactive alkyd surfactant and stable emulsions made therefrom
EP3024874B1 (en) Novel polymers and use of these as dispersants
CN105473628B (en) Bonding enhancing additive and the coating composition containing the additive
CN102844354B (en) Polymer dispersion comprising highly branched polycarbonate with unsaturated fatty acid groups
EP3215558A1 (en) Novel polymer compositions and use of these polymer compositions as dispersants
EP3535307B1 (en) Novel monomers and polymers
US20070142591A1 (en) High temperature polymerization process for making caprolactone-modified branched acrylic polymers
WO2016096816A1 (en) Novel polymer compositions and use of these polymer compositions as viscosity modifiers
US10717800B2 (en) Controlled crosslinking of latex polymers with polyfunctional amines

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130424

Termination date: 20141119

EXPY Termination of patent right or utility model